C o n t e n t s

Introduction

1.1

1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
1.10
1.11
1.12
1.13

Composites - General Introduction

Historical Background
Classification of Composites
Short fiber- Rubber Composites
Constituents of short fiber-rubber composites
Reinforcing Mechanism of Short Fibers
Factors affecting the properties of Short fiber- Rubber Composites
Multicomponent system
Nanocomposites
Silica
Application of Nanosilica / Short fiber / Elastomeric hybrid Composites
Scope and objectives of the present work
References

Composites - General Introduction

Composites are one of the most advanced and adaptable engineering

materials known to men. Progresses in the field of materials science and

technology have given birth to these fascinating and wonderful materials.
Composites are heterogeneous in nature, created by the assembly of two or more
components with fillers or reinforcing fibers and a compactable matrix [1]. The
matrix may be metallic, ceramic or polymeric in origin. It gives the composites
their shape, surface appearance, environmental tolerance and overall durability
while the fibrous reinforcement carries most of the structural loads thus giving
macroscopic stiffness and strength [2]. A composite material can provide superior
and unique mechanical and physical properties because it combines the most
desirable properties of its constituents while suppressing their least desirable
properties. At present composite materials play a key role in aerospace industry,
automobile industry and other engineering applications as they exhibit outstanding

Chapter-1

strength to weight and modulus to weight ratio. High performance rigid composites
made from glass, graphite, kevlar, boron or silicon carbide fibers in polymeric
matrices have been studied extensively because of their application in aerospace
and space vehicle technology [3-8].
Based on the matrix material which forms the continuous phase, the
composites are broadly classified into metal matrix (MMC), ceramic matrix (CMC)
and polymer matrix (PMC) composites. Of these, polymer matrix composites are
much easier to fabricate than MMC and CMC. This is due to the relatively low
processing temperature required for fabricating polymer matrix composite. PMCs
generally consist of synthetic fibers like carbon, nylon, rayon or glass embedded in
a polymer matrix, which surrounds and tightly binds the fibers. Typically, the
fibers make up about 60 % of a polymer matrix composite by volume. The
structure, properties and applications of various composites are being investigated
world wide by several researchers [9 -18].
The fibrous reinforcing constituent of composites may consist of thin continuous
fibers or relatively short fiber segments. When using short fiber segments, fibers with
high aspect ratio (length to diameter ratio) are used. Continuous fiber reinforced
composites are generally required for high performance structural applications. The
specific strength (strength to density ratio) and specific stiffness (modulus to density
ratio) of continuous carbon fiber reinforced composites can be superior to conventional
metal alloys. Also depending upon how fibers are oriented within the matrix, composites
can be fabricated into products that have structural properties specifically tailored for a
particular use. Polymer concretes are increasingly being used in buildings and other
structures. They represent a new type of structural material capable of withstanding
highly corrosive environments. The high strength to weight ratio and non-corrosive
characteristics of these materials like fiber-reinforced plastics can be utilised to build
innovative structures, which are, desirable and economical [19].

Introduction

Although composite materials have certain advantages over conventional

materials, they have some disadvantages also. PMCs and other composite
materials tend to be anisotropic; that is, properties like strength, stiffness etc. are
different in different directions depending on the orientation of composite
constituent materials. These anisotropic properties pose a significant challenge for
the designer who uses composite materials in structures that place multi-directional
forces on structural members. Also formation of a strong connection between the
components of the composite material is difficult. The broader use of advanced
composites is inhibited by high manufacturing costs. Development of advanced
composite materials having superior mechanical properties opened up new
horizons in the engineering field. The advantages such as corrosion resistance,
electrical insulation, low thermal expansion, higher stiffness, strength and fatigue
resistance make them preferred candidates for many applications [20-25].

1.2

Historical Background
Nature has provided composite materials in living things such as seaweeds,

bamboo, wood and human bone. The first reinforced polymeric based materials appear
to have been used by the people of Babylonia around 4000-2000 B.C. The materials
consisted of reinforced bitumen or pitch. Around 3000 B.C. evidences from various
sources indicate that in Egypt and Mesopotamia, types of river-boat were constructed
from bundles of papyrus reed embedded in a matrix of bitumen. The art of
mummification that flourished in Egypt during 2500 B.C.exemplifies one of the first
filament winding process. Suitably treated dead bodies were wrapped in tapes of linen
and then impregnated with a natural resin to produce, ultimately a rigid cocoon. The
use of lac has been known to India and China for several thousands of years. It is
recorded in the Vedas written about 1000 B.C. In India the resin was used as filling for
swords hafts and in the manufacture of whetstones by mixing shellac with fine sand.
The latter example may be considered as the forerunner of the modern composite

Chapter-1

grinding wheel. By 500 B.C., the Greeks were building ships with three banks of oars
called triremes. They possessed keels that were much longer than could have been
accomplished by using a single length of timber. Thus, it can be seen that the origin of
composite technology goes back into antiquity.
The relative importance of the structural materials most commonly used, i.e.
metals, polymers, composites, and ceramics, to various societies throughout history has
fluctuated. Ashby [26] presents a chronological variation of the relative importance of
each group from 10,000 B.C. and extrapolates their importance through the year 2020.
The information contained in Ashbys article has been partially reproduced in Figure
1.1. The importance of composites has experienced a steady growth since about 1960
and is projected to continue to increase through the next several decades.
The fiber-reinforced polymer market is estimated at almost 1.04 million metric
tons (2.3 billion lbs) in 2002, and is expected to increase by 15 % in volume [27].
According to the above report, the market for fiber-reinforced polymers will grow at an
average annual growth rate (AAGR) of 3.0 % through the next five years, increasing to
1.2 million tons per year by 2010.

Figure 1.1. Relative importance of material development through history

4

Introduction

1.3

Classification of Composites
Based on the types of reinforcement used, the composites are classified as

1.3.1 Particulate reinforced composites

A composite whose reinforcement is a particle with all the dimensions
roughly equal are called particulate reinforced composites. Particulate fillers are
employed to improve high temperature performance, reduce friction, increase wear
resistance and to reduce shrinkage [28]. The particles will also share the load with
the matrix, but to a lesser extent than a fiber. A particulate reinforcement will
therefore improve stiffness but will not generally strengthen.
1.3.2 Fiber reinforced composites
Fiber reinforced composites contain reinforcements having lengths higher
than cross sectional dimension. Fibrous reinforcement represents physical rather
than a chemical means of changing a material to suit various engineering
applications [29]. These can be broadly classified as

Chapter-1

Reinforcing fiber in a single layer composite may be short or long based on

its overall dimensions. Composites with long fibers are called continuous fiber
reinforcement and composite in which short or staple fibers are embedded in the
matrix are termed as discontinuous fiber reinforcement (short fiber composites). In
continuous fiber composites fibers are oriented in one direction to produce
enhanced strength properties. In short fiber composites, the length of short fiber is
neither too high to allow individual fibers to entangle with each other nor too small
for the fibers to loss their fibrous nature. The reinforcement is uniform in the case
of composites containing well dispersed short fibers. There is a clear distinction
between the behavior of short and long fiber composites.
1.3.3 Hybrid composites
Composite materials incorporated with two or more different types of fillers
especially fibers in a single matrix are commonly known as hybrid composites.
Hybridisation is commonly used for improving the properties and for lowering the
cost of conventional composites. There are different types of hybrid composites
classified according to the way in which the component materials are incorporated.
Hybrids are designated as i) sandwich type ii) interply iii) intraply and iv)
intimately mixed [30]. In sandwich hybrids, one material is sandwiched between
layers of another, whereas in interply, alternate layers of two or more materials are
stacked in regular manner. Rows of two or more constituents are arranged in a
regular or random manner in intraply hybrids while in intimately mixed type, these
constituents are mixed as much as possible so that no concentration of either type is
present in the composite material.
1.3.4 Laminates
A laminate is fabricated by stacking a number of laminae in the thickness
direction. Generally three layers are arranged alternatively for better bonding
between reinforcement and the polymer matrix, for example plywood and paper.
6

Introduction

These laminates can have unidirectional or bi-directional orientation of the fiber

reinforcement according to the end use of the composite. A hybrid laminate can
also be fabricated by the use of different constituent materials or of the same
material with different reinforcing pattern. In most of the applications of laminated
composite, man made fibers are used due to their good combination of physical,
mechanical and thermal behavior.

1.4

Short fiber- Rubber Composites

The term short fiber means that the fibers in the composites have a critical

length which is neither too high to allow individual fibers to entangle with each
other, nor too low for the fibers to lose their fibrous characteristics. A short fiber
composite signifies that the two main constituents, i.e., the short fibers and the
rubber matrix remain recognizable in the designed material. When used properly,
a degree of reinforcement can be generated from short fibers, which is sufficient
for many applications.

Interface
Fiber

Matrix

Figure 1.2. Short fiber composite

Short fiber reinforced rubber composites were developed to fill the gap between
the long fiber reinforced and particulate filled rubber composites. That is mainly to
achieve the high performance of the fiber coupled with easy processability and

Chapter-1

elasticity of the rubber. Composites in which the short fibers are oriented uniaxially in
an elastomer have a good combination of good strength and stiffness from the fibers
and elasticity from the rubber. These composites are being used for the fabrication of a
wide variety of products such as V-belts, hoses and articles with complex shapes [3132]. Short fiber reinforced rubber composites possess several advantages over
continuous fiber composites [33-36]. Short fibers can be easily incorporated into the
rubber compound along with other ingredients. They are amenable to standard rubber
processing operations such as extrusion, calendaring, compression molding, injection
molding etc. These composites provide high green strength and high dimensional
stability during fabrication. Design flexibility is another advantage of these composites.
Complex shaped articles which is quite difficult to accomplish with long fiber
composites can be fabricated using short fiber composites. Mechanical properties like
specific strength and stiffness, reduced shrinkage in molded products, resistance to
solvent swelling, abrasion, tear and creep resistance are greatly improved in the case of
short fiber composites. Moreover short fibers are cheaper than long fibers. But there
are some disadvantages also. Difficulty in achieving uniform dispersion, fiber breakage
during processing, difficulties in handling and bonding etc. are some among them.
One of the first reports on short fiber reinforcement of rubber, natural rubber
was used by Collier [37] as the rubber matrix, which was reinforced using short
cotton fibers. Though NR, the most commonly used elastomeric matrix for short
fiber reinforcement, styrene butadiene rubber (SBR), chloroprene rubber (CR),
nitrile rubber (NBR) and ethylene propylene rubber (EPDM) also received
attention [38- 44].These rubbers were reinforced using short fibers such as cotton,
silk, rayon,jute and Nylon [45- 50].
Mingtao Run et al. [51] studied crystal morphology and nonisothermal
crystallization kinetics of short carbon fiber/ poly(trimethylene terephthalate)
composites. Relationship between processing method and microstructural and

Introduction

mechanical properties of poly(ethylene terephthalate) / short glass fiber composites

were studied by Mondadori et.al. [52]. Das et al. [53] reinforced bromobutyl rubber
using short Kevlar fiber. Zuev [54] studied the mechanical properties of fiber-filled
rubber composites and ways of effective utilization of mechanical properties of fibers
in fiber filled rubber composites and compared with those of rubber compound in the
absences of fibers. Maya et al. [55] presented a review on cellulosic fiber-reinforced
green composites. Short Nylon fiber reinforced polypropylene was studied by
Thomas et al.[56]. Anuar and co workers [57] studied the tensile and impact
properties of thermoplastic natural rubber reinforced short glass fiber and empty fruit
bunch hybrid composites. In a review, Kun [58] presented the effect of type of fiber,
fiber pretreatment, compounding and processing on the product performance
properties. Advances in short fiber pretreatment, interfacial adhesion and
development of short fiber- rubber composite products were reviewed by Zhou et al.
[59]. Fiber reinforced plastic and rubber composites for electrical insulators have
been manufactured by Kadowaki [60].
Wazzan [61] studied the physico-mechanical properties of EPDM/ Nylon-6
short fiber composites. Dynamic mechanical behavior of short coir fiber reinforced
natural rubber composites was studied by Geethamma et al. [62]. In the case of soft
rubbery composites cellulose fiber has been found to give better reinforcement than
glass or carbon fibers [63]. Atomic force microscopy (AFM) studies of short
melamine fiber reinforced EPDM rubber was done by Rajeev et al.[64]. Short jute
fiber reinforced NR composites have been studied by Murty et al.
[65].Investigations have also been made on short jute fiber reinforced carboxylated
nitrile rubber [66]. Cure characteristics and mechanical properties of short Nylon 6
fiber nitrile rubber composites were studied by Rajesh et al. [67]. Natural rubbercoir fiber composite was studied by Geethamma et al [68-69]. A novel method for
the preparation of short Nylon fiber-natural rubber composites was developed by
Bipinbal et al. [13], in which short fibers chopped to approximately 6 mm were
9

Chapter-1

incorporated in the latex stage and processed into sheet form. By this method,
mixing cycle time was reduced without compromising the fiber dispersion. Fiber
breakage during mixing was also reduced. Effect of processing parameters on the
mechanical properties of short Kevlar aramid fiber- thermoplastic PU composite
were reported by Kutty et al. [70]. Kutty et al. [71] also studied the reinforcement
of millable PU with short Kevlar fiber. The mechanical properties of short fiber
polymer composites and the influence of surface treatment of short fiber have also
been investigated [72-75].The possibility of using natural fibers as reinforcement in
polymer based composites has been examined [76-80]. Studies on composites
containing short banana fibers and polyester resin have been conducted [81-83].
Effect of short fiber diameter on mechanics of rubber composites was studied by
Zhang et al. [84]. Rheological properties of short polyester fiber polyurethane
elastomer composites with and without bonding agent was reported by Suhara et al.
[85 - 86]. Suhara et al. [87] also studied the thermal degradation of short polyester
fiber- polyurethane elastomer composite and found that incorporation of short fiber
enhanced the thermal stability of the elastomer.

1.5

Constituents of Short Fiber-Rubber Composites

1.5.1 Rubber matrix

Various elastomers have been used as matrices for short fiber reinforcement.
Typically, the matrix has considerably lower density, stiffness and strength than
those of the reinforcing fiber material, but the combination of matrix and fiber
produces high strength and stiffness, while still possessing a relatively low density.
In a composite the matrix is required to fulfill the following functions:

To bind together the fibers by virtue of its cohesive and adhesive

characteristics

10

To protect them from environments and handling.

Introduction

To disperse the fibers and maintain the desired fiber orientation and spacing.

To transfer stresses to the fibers by adhesion and / or friction across the fibermatrix interface when the composite is under load, and thus to avoid any
catastrophic propagation of cracks and subsequent failure of the composites.

To be chemically and thermally compatible with the reinforcing fibers.

To be compatible with the manufacturing methods which are available

to fabricate the desired composite components.

1.5.1.1 Natural rubber (NR)

Natural rubber is a high molecular weight polymer of isoprene in which
essentially all the isoprenes have the cis 1-4 configuration. The chemical structural
formula of natural rubber is shown in figure 1.3.

Figure 1.3. Structural formula of Natural Rubber

Among various rubbers, natural rubber is very important since it possess the
general features of other rubbers in addition to the following highly specific
characteristics. Since it is of biological origin, it is renewable, inexpensive and
creates no health hazard problems. It possesses high tensile strength due to strain
induced crystallization. It also possesses superior building tack and good crack
propagation resistance. Apart from the conventional rubber products, NR finds a
few specialized applications. NR is a versatile and adaptable material which has
11

Chapter-1

been successfully used for transport and engineering applications such

automobile tyres, aero tyres, off-the-road and aerospace industries, civil
engineering, railways, vibration engineering etc.
Reinforcement of NR using particulate fillers and short fibers has been
studied at length [88-90]. Cure characteristic and mechanical properties of
natural rubber short Nylon fiber composites were studied by Sreeja et al. [48].
Atsushi et al.[91] studied about the nanostructure in traditional composites of
natural rubber and reinforcing silica. Yoshitaka and co workers [92] investigated
the friction of short fiber-reinforced rubber on wet surfaces. Sisal and short
pineapple fibers have been used for reinforcement of NR [93-97].
1.5.1.2 Styrene butadiene rubber (SBR)
Styrene butadiene rubber (SBR) is a non-polar synthetic rubber that is the
most commonly used general-purpose synthetic rubber. SBR is a copolymer of
styrene and butadiene. Some of the properties of SBR are inferior to that of NR.
The green strength, heat build up and tackiness are some examples. It is marketed
generally at a lower viscosity than NR and this permits its use in industry without
pre-mastication. Abrasion resistance and resistance to degradation under heat are
better for SBR than NR. SBR finds applications in tyres, shoe soles, foot wear
components, insulation of wires and cables, carpet backing etc Effect of filler
content on the mechanical properties of SBR was studied and results showed that
the properties improved with filler loading [98-100]. Thermal degradation of short
Nylon fiber reinforced SBR composite was studied by Seema et al.[101]. Seema
[102] also studied the rheological characteristics of short Nylon 6 fiber reinforced
SBR containing epoxy resin as bonding agent. Praveen and co workers [23] studied
the effect of filler geometry on viscoelastic damping of graphite/aramid and carbon
short fiber-filled SBR composites.

12

Introduction

1.5.1.3 Acrylonitrile butadiene rubber (NBR)

Acrylonitrile Butadiene Rubber (Nitrile rubber) is a copolymer of
acrylonitrile and butadiene and it is a polar specialty rubber. NBR has good
resistance to a wide variety of oils and solvents and hence is widely used for
products like oil seals, pipe protectors, blow out preventors etc. [103]. Major
properties of NBR depend on the acrylonitrile content (ACN) which usually vary
from 20-50% by weight. Commercially available nitrile rubbers differ from one
another in three respects: acrylonitrile content, polymerization temperature and
Mooney viscosity. NBR has high viscosity that can be reduced by mastication. The
physical and mechanical properties of NBR reinforced with different fillers have
been studied [104-106]. Short fiber reinforced NBR composites were studied by
Yoshiki and Sreeja [107-108]. Seema et al. studied the effect of an epoxy-based
bonding agent on the cure characteristics and mechanical properties of short Nylon
fiber reinforced NBR composite [109]. Thermal degradation of melamine fiber
reinforced NBR composite was studied by Rajeev et al. [110]. Wang et al.[111]
found that nitrile rubber exhibited the highest interaction with silica probably
through the hydrogen bond between the CN group and silanol groups. Property
optimization in nitrile rubber composites via hybrid filler systems was studied by
Nugay [112].
1.5.1.4 Chloroprene rubber (CR)
Chloroprene rubber (Neoprene) also comes under the category of specialty
rubbers. This rubber is used in specific applications which require solvent
resistance, fire resistance and thermal resistance. Neoprene does not require
sulphur for vulcanization. Its general physical properties are enhanced by
compounding it with metallic oxides such as ZnO and MgO. Polychloroprenes
heat and flex resistance make it an excellent choice for application such as
industrial and automotive hoses, V- belts, transmission belts, conveyor belts,
escalator hand rails, motor mountings, wire and cables and adhesives. Neoprene
13

Chapter-1

also received much attention of many researches [113-115]. Effects of fiber loading
and matrix strength on physical properties of the short aramid fiber reinforced
chloroprene rubber composite was investigated by Park and co workers [116].
Butadiene rubber (BR), ethylene propylene rubber (EPR), Butyl rubber (IIR),
polyacrylic rubbers, fluorocarbon rubbers, silicone rubbers and polyurethane rubbers
were also used as matrix materials for short fiber reinforcement [61,117-124]. Many
researchers used rubber-rubber and rubber-plastic blends as matrix materials for
short fiber composites. Boustany et al.[125] used NR-SBR blends as the matrix in
the short fiber reinforcement using cellulose fiber. A 50/50 blend of ethylene vinyl
acetate and EPDM reinforced using short carbon fibers was studied by Das et al.
[126]. Zhang et al. [127] prepared short sisal fiber reinforced epoxidized natural
rubber/ polyvinyl chloride blend. Zebarjad et al. [128] observed that the
modification of PP with a combination of EPDM rubber and glass fiber could be
used for improving the mechanical properties of the plastics. Arroyo and Bell [129]
studied the effect of short aramid fibers on the mechanical behavior of isotactic PP
and EPDM rubber and their blends. Sreeja and Kutty [130-131] prepared natural
rubber-whole tire reclaim-short Nylon fiber composites and studied the effect of
urethane based bonding agent on the cure characteristics and mechanical
properties.
1.5.2 Fiber reinforcement
Fiber is defined as any single unit of matter characterized by flexibility,
fineness and high aspect ratio [132]. It is a slender filament that is longer than 100
m or the aspect ratio greater than 10. Fibers have a fine hair like structure and
they are of animal, vegetable, mineral or synthetic origin [133]. Fibers are broadly
classified into types as natural and man made or synthetic.

14

Introduction
Fibers

Natural

Vegetable

Animal

Man Made

Mineral

Regenerated

Synthetic

Fiber reinforced rubber compounds play a crucial role in high pressure hoses,
transmission belts, conveyor belts and tires. Until about 1890, only natural fibers
were available. Just before the end of the 19 th century the first synthetic fiber based
on cellulose, rayon was developed. These cellulose yarns are considered to be half
synthetic, because the raw material is still a natural polymer, cellulose. DuPont
developed the first fully synthetic fiber Nylon 66, it was commercially introduced
in 1936 (Carothers). A few years latter, Nylon 6 (Schlack, 1941) and polyester
(Whinfield & Dickson, 1942) were introduced. The development of advanced
fibers took place around 1970. Most of these fibers were produced from fully
aromatic polymers with high temperature stability. Eventually this led to the
discovery of the liquid crystalline PPTA (paraphenylene terephthalamide), the first
super strong fiber (DuPont and Akzo Nobel). The second super strong fiber was gel
spun poly ethylene, Dyneema of DSM, introduced in 1979.
1.5.2.1 Natural fibers
Extensive research has been done on the reinforcement of elastomers using
natural fibers. The reinforcement of elastomers using cellulose fiber was studied by
different authors [134-139]. Jute and silk fibers were also added to different rubber
matrices for the preparation of short fiber rubber composites [65, 140-143]. Sisal,
coir, coconut and pineapple leaf fibers were also used to reinforce various
elastomeric matrices [69, 94, 96, 124,127,144-145].

15

Chapter-1

1.5.2.2 Synthetic fibers

(a) Glass fiber
Glass fiber is the best known reinforcement in high performance
composite applications due to its appealing combination of good properties and
low cost. The major ingredient of glass fiber is silica which is mixed with
varying amounts of other oxides. The different types of glass fibers
commercially available are E and S glass. The letter E stands for electrical
as the composition has a high electrical resistance and S stands for strength.
Glass fibers are used successfully for reinforcing the plastics and therefore, the
suitability of this fiber as a reinforcing material for rubbers has been studied.
High initial aspect ratio can be obtained with glass fibers, but brittleness causes
breakage of fibers during processing. Czarnecki and White [146] reported the
mechanism of glass fiber breakage and severity of breakage with time of
mixing. Rubber latex also reinforced using glass fibers [147-148]. Gregg [149]
reported that the tensile strength of glass fiber-rubber composite decreased with
increased atmospheric humidity during glass fiber storage. Marzocchi [150]
developed glass fiber-elastomer composites with improved strength and wear
resistance to be used in auto tires, V-belts and conveyor belts. Murty and coworkers [136, 151-152] studied the extent of fiber-matrix adhesion and physical
properties of short glass fiber reinforced NR and SBR composites. Oh and Joo
[153] reported the effect of glass fiber dimension on the mechanical properties
of glass fiber reinforced PP/EPDM blends.
(b)

Carbon fibers

Carbon fiber is the one of the important high performance fiber used in
short fiber-polymer composite. They are commercially manufactured from three
different precursors rayon, polyacrylonitrile (PAN) and petroleum pitch. They
are mainly used in aerospace industry due to its outstanding mechanical
properties combined with low weight. Though carbon fibers are extensively
16

Introduction

used in polymer composites, its application in rubber matrices is limited to

specific end use, mainly in electrically conductive composites. Yagi and coworkers [154] were granted a European Patent for the invention of highly
conductive carbon fibers for rubber and plastics composites. They dispersed
fibers in the matrix by kneading. Jana and co-workers [155 -156] studied the
electrical conductivity of randomly oriented carbon fiber-polymer composites.
Das et al. [126,157-158] reported the various aspects of electrical conductivity
of short carbon fiber reinforced EVA, EPDM and their blends. Pramanik et al.
[159-160] studied the resistivity of short carbon fiber reinforced nitrile rubber
composites. The effect of incorporation of short carbon fiber in the
thermoplastic elastomers was studied by Correa et al. [161], Roy and coworkers [162-164] Shonaike and Matsuo [165] and Ibarra et al. [166-167]. The
effect of short carbon fibers on the anisotropic, swelling, mechanical and
electrical properties of radiation cured SBR rubber composites were studied by
Abdel-Aziz et al. [168]. Older and Kumar [169] developed an ablative materials
for solid propellant rocket motor using carbon fiber and rubber matrix. A tire
tread compound composed of silica, carbon black and carbon fiber was
developed by Verthe et al. [170].
(c)

Aramid fibers

Aramid is a generic term for aromatic polyamide fibers. The first

commercial p- aramid fiber (Kevlar) was introduced in 1971 [171]. Several aspects
of aramid fiber reinforcement of elastomeric matrices and thermoplastic elastomers
were discussed by various authors [172-176]. Sunan et al. [177] compared the
reinforcing effect of as received and hydrolysed Kevlar fiber reinforced
thermoplastic elastomer (Santoprene) composites.

17

Chapter-1
(d)

Nylon fibers

Nylons are aliphatic polyamides, which was the first synthetic fiber to be
commercialized (1939). Nylons are derived from a diamine and a dicarboxylic
acid. Because a variety of diamines and dicarboxylic acid can be produced, there
are very large number of polyamide materials available to prepare Nylon fibers.
The most common versions are Nylon 66 and Nylon 6. Nylon 66 which is widely
used as fiber is made from adipic acid and hexamethylene diamine. The
commercial production of Nylon 6 begins with carprolactum. Nylon fiber has
outstanding durability and excellent physical properties. The main features are
exceptional strength, high elastic recovery, abrasion resistance, lusture,
washability, resistance to damage from oil and many chemicals, high resilience,
colourability, smooth, soft and long lasting fibers from filament yarn, light weight
and warm fabrics from spun yarn. Like polyester fiber, Nylon has high melting
point which conveys good high temperature performance. Table1.1 gives the
typical physical properties of Nylon fibers.
The reinforcement of rubbers using Nylon fibers was reported by various
authors [13,101-102]. Cure characteristic and mechanical properties of short
Nylon fiber reinforced NBR and CR composite containing Epoxy based
bonding agent was investigated by Seema et al. [109,113]. Physico-mechanical
properties of EPDM/ Nylon 6 short fiber composite was studied by Wazzan
[61].

Senapati et al. [178] studied the effect of short Nylon fiber on the

mechanical properties of NR vulcanizates. Sreeja et al. [48, 108, 179] studied

short Nylon 6 fiber reinforced NR, NBR, SBR composite and found that short
Nylon 6 fiber enhanced the mechanical properties of those rubbers. Dynamic
viscoelastic properties of Nylon short fiber reinforced elastomeric composites
were studied by Chen et al. [180].

18

Introduction

Table 1.1. Typical physical properties of Nylon fibers

Property

Continuous filament

Staple

0.40 - 0.71

0.35 - 0.44

15 - 30

30 - 45

3.5

3.5

4.0 - 4.5

4.0 - 4.5

Specific Gravity

1.14

1.14

Approx.volumetric swelling in
water,%

2 - 10

2 - 10

Tenacity at break
N / tex, 65 % RH, 21 oC
Extension at break,
%, 65 % RH, 21 oC
Elastic modulus
N / tex, 65 % RH, 21 oC
Moisture regain (%)
65 % RH, 21 oC

Short Nylon fiber reinforced SBR composites for V-belt applications were
reported by King et al. [181]. Ye et al. [182] incorporated short Nylon fiber into SBR
and BR matrices and reported that the vulcanization time increased with fiber
content. Seema et al. [101,104] also reported the thermal degradation of short Nylon
6 fiber reinforced NBR and SBR composites. Short Nylon fiber and vinylon fiber
reinforced nitrile rubber and SBR were studied by Zhou et al. [183]. They also
studied the effect of fiber pretreatment on properties of short Nylon fiber-rubber
composites [184-185]. They introduced an effective interfacial thickness concept
based on Halpin Tsai equation to characterize the fiber-rubber interfaces. The
reinforcement and orientation behavior of short Nylon fibers in NR, SBR and CR
were studied with emphasis on the determination of ideal aspect ratio for fibers by
Bhattacharya [186]. Mechanical properties of short Nylon fiber reinforced SBR/NR
composites were studied in detail by Ma et al.[187]. Zhang et al. [188] studied the
influence of loading level of Nylon fiber in NR and polyester fiber in CR and
proposed a model to calculate the structure of interfacial layer. Rajesh et al. [67]

19

Chapter-1

studied the cure and mechanical properties of short Nylon fiber NBR composites.
The influences of fiber length, loading and rubber crosslinking systems on the
properties of the composites were analysed. Processing parameters of short Nylon 6
fiber reinforced SBR composites with respect to the effect of shear rate, fiber
concentration and temperature on shear viscosity and die swell was studied by
Seema and Kutty [189].

1.6

Reinforcing Mechanism of Short Fibers

The reinforcing mechanism of fiber in a unidirectional composite can be

explained as follows. The composite satisfies the equation 1.1 when a tensile or
compressive load is applied parallel to the fiber direction. This equation is
applicable under perfect conditions of adhesion between fiber and matrix [190].

c = f = m
where c ,

and

................................................ (1.1)

m are the strain in composite, fiber and matrix respectively. If it

is assumed that both fibers and matrix behave elastically, then the following equations
can be applied.

f = Ef f

...................................................(1.2)

m = Em m

...................................................(1.3)

Hence

c / Ec = m / Em = f / Ef

...................................................(1.4)

where c, f and m are stress developed in composites, fiber and matrix

respectively. Similarly, Ec, Ef and Em are the modulus of composites, fiber and
matrix, respectively. Generally Ef is greater than Em and so the stress in the fiber is
greater than that in the matrix. Thus the fiber can bear a major part of the applied
load. In the analysis of long fiber- reinforced composites, any effect associated

20

Introduction

with fiber ends are neglected. But in the case of short fiber reinforced composites,
the end effects become progressively significant due to the decrease in aspect ratio
of the fiber. This result in the reduction of fiber efficiency in reinforcing the matrix
and also causes an early fracture of the composite.

(a). Continuous fiber composite deformed

(b). Short fiber composite un-deformed

(c). Short fiber composite deformed

Figure 1.4. Effect of stretching force on the strain around long and
short fiber in a low modulus matrix

Consider an oriented fiber composite in which fibers are aligned parallel to

the direction of application of force. A single fiber is embedded in a matrix of
lower modulus. Imagine perpendicular lines running through the fiber - matrix
interface in a continuous manner in the unstressed state as shown in the figure
1.4(b). The matrix and the fiber will experience different tensile strains because of
their different moduli. When the composite is loaded axially, the longitudinal strain
in the matrix will be higher than that in the adjacent fiber due to lower modulus of
the former. When force is applied, the imaginary vertical lines in the continuous

21

Chapter-1

fiber composite will not be distorted (Fig.1.4(a)). But these lines in short fiber
composite will be distorted as in figure 1.4(c) because at the region of fiber ends,
the matrix will be deformed more than that in the region along the fiber. This
difference in the longitudinal strains creates a shear stress distribution around the
fibers in the direction of the fiber axis and so the fiber is stressed in tension. The
applied load is transferred from matrix to fiber across the interface because of this
shear stress distribution.
When mechanical force is applied to the polymeric matrix, it spreads
smoothly through the matrix until it reaches the matrix- fiber interface. If the
interface is well bonded, the stress is transferred across it into the fiber and then
spread throughout the fiber. This process occurs at all the fiber- matrix interfaces in
the composite. Thus it is obvious that load will be transferred to the fiber only if the
interface is strong and a perfect bond exists between the two constituents. Hence
strong interface is a must for high reinforcing efficiency.

1.7

Factors affecting the properties of Short fiber- Rubber Composites

1.7.1 Type and fiber breakage

The importance of fiber length and its influence on the properties of the
composites were studied by several researchers [191-194]. In a composite
material fiber length is a critical factor which should not be too long so that
they entangle with each other causing problems of dispersion. But a very small
length of fiber does not offer sufficient stress transfer from the matrix to the
fiber. The severity of fiber breakage mainly depends on the type of fiber and its
initial aspect ratio. Fibers like glass and carbon are brittle and they posses a low
bending strength than Nylon fiber which are more flexible and resistant to
bending. For each type of fiber there exists a certain aspect ratio below which
no further breakage can occur depending on its resistance to bending. If the mix
viscosity is high, more shear will be generated during mixing and thus

22

Introduction

exceeding the critical bending stress of the fiber which eventually results in
severe breakage. OConnar [195] has reported the fiber breakage during mixing.
Murthy and De [151] suggested that the breakage of the fiber is due to the
buckling effect. De et al. [142-143,196] have studied the breakage of jute and
silk fibers in NR and NBR and found that the breakage of silk fibers is less than
that of jute fibers. Considerable fiber breakage occurred during mixing of fibers
with high aspects ratio (as high as 500) resulting in reduction in aspects ratio
[197]. Noguchi et al. [198] reported that short PET fibers did not break up
during the milling process and they are well dispersed, but carbon fibers did
break up during milling, the fiber length being reduced to about 150 m.
Significant breakage of short Kevlar fibers during mixing in Brabender
plasticorder in TPU matrix was reported by Kutty et al. [70,199].
1.7.2 Critical fiber length and aspect ratio of fiber
The fiber ends in the short fiber reinforced composites play a major role in
the determination of ultimate properties of the composite. The concept of critical
fiber length over which the stress transfer allows the fiber to be stressed to its
maximum, or at which efficient fiber reinforcement can be achieved has been used
to predict the strength of the composites. Broutmann and Agarwal [191] have done
a theoretical analysis on the mechanism of stress transfer between matrix and fiber
of uniform length and radius and have given the following expression for the
critical fiber length (lc).

lc/d = fu/2y

............................................................... (1.5)

where d is the diameter of the fibre, fu is the ultimate fiber strength, and y is the
matrix yield stress in shear. The aspect ratio (the length to diameter ratio) (l/d) of
fibers is a major parameter that controls the fiber dispersion and fiber matrix
adhesion that gives the optimum performance of short fiber polymer composites. If

23

Chapter-1

the aspect ratio of the fiber is lower than the critical aspect ratio, insufficient stress
will be transferred and the reinforcement will be inefficient. Several researchers
[142,200-202] have suggested that an aspect ratio in the range of 100-200 is
essential for high performance fiber- rubber composites for good mechanical
properties. However Chakraborthy [143] has observed that an aspect ratio of 40
gives optimum reinforcement in the case of carboxylated nitrile rubber composite
reinforced with jute fiber. Murthy and De [65,203] have reported that an aspect
ratio of 15 and 32 are sufficient for reinforcement of jute fiber in NR and SBR
respectively. It was reported that for synthetic fiber like polyester and Nylon
aspect ratios of 220 and 170, respectively give good reinforcement in natural
rubber vulcanizates [204-205]. Hong Gun Kim [206] investigated the effects of
fiber aspect ratio in short fiber reinforced composites.
1.7.3 Fibre orientation
Fiber orientation has a significant influence on the physico mechanical
properties of short fiber reinforced rubber composites [207-208]. The preferential
orientation of fibers in the matrix results in the development of anisotropy in the
matrix. With respect to orientation two limits are explained as longitudinal (along
machine direction) and transverse (across machine direction), as given in figure
1.5. It was observed that during mixing procedure lower the nip gap, higher the
anisotropy in tensile properties of the composites implying greater orientation of
fibers. This is represented as anisotropy index, which reduces gradually with
increasing nip gap. Akthar et al. [209] found a small nip gap and single pass in the
mill to be the best. During processing and subsequent fabrication of short fiber
polymer composites, the fibers orient preferentially in a direction depending upon
the nature of flow i.e., convergent and divergent as explained by Goettler [210]. If
the flow is convergent the fibers align themselves in the longitudinal direction and
if it is divergent they orient in the transverse direction.

24

Introduction

Figure 1.5. Schematic representation of the (1) longitudinal

(2) transverse orientation of the fibers in the rubber matrix

In longitudinally oriented composites the effective stress transfer from the

matrix to the fiber occurs in the direction of fiber alignment and greater strength
and reinforcement will be experienced by the composite. In transversely oriented
composites the stress transfer takes place in a direction perpendicular to the fiber
alignment and hence fracture of the sample occurs at a lower tensile stress which
may be equal or lower than the strength of the matrix. Recently Thomas and co
workers [68] have evaluated the percentage (%) extent of orientation from green
strength measurements, by using the following equation

Orientation %

S L /SG , L
S L /SG + ST /SG

...................................................(1.6)

where S represents green strength of the composite and subscript L, T denotes

longitudinal and transverse orientation, respectively and G represents the gum
25

Chapter-1

compound. Many researchers have used SEM to study the fractured surface to
determine the fiber orientation [211-212]. Senapati et al. [213] reported that two
passes through tight nip gave optimum mechanical properties for short PET/NR
composites. The effect of mill opening and the friction ratio of the mill and
temperature of the rolls on the orientation of short Kevlar fibers in TPU matrix has
been described by Kutty et al. [70].
1.7.4 Fiber dispersion
Good dispersion of short fibers in the rubber compounds is an essential
requisite for high performance composites. The naturally occurring cellulosic fibers
tend to agglomerate during mixing due to hydrogen bonding. A pretreatment of
fibers at times is necessary to reduce fiber-fiber interactions. Natural fibers treated
either with carbon black or compositions containing latex were found to be
dispersing well in the rubber matrix [214]. Fiber length has also a role in
facilitating better dispersion. Derringer [215-216] has used commercially available
fibers such as Nylon, rayon, polyester and acrylic flock cut into smaller lengths of
4mm to study dispersion.
1.7.5 Fiber concentration
Concentration of fibers in the matrix plays a crucial role in determining the
mechanical properties of the fiber reinforced polymer composites. A lower
concentration of fibers gives lower mechanical strength. This has been observed
not only in rubbers [217] but also in thermoplastic elastomeric matrices
[162,199,213,218]. This behavior has been attributed basically to two factors, (a)
dilution of the matrix which has a significant effect at low fiber loadings and (b)
reinforcement of the matrix by the fibers which becomes increasingly important as
fiber volume fraction increases. At low fiber content, the matrix is not restrained by
enough fibers and highly localized strains occur in the matrix at low strain levels
causing the bond between fibers and the matrix to break, leaving the matrix diluted

26

Introduction

by non reinforcing debonded fibers. At high fiber concentrations, the matrix is

sufficiently restrained and stress is more evenly distributed thus the reinforcement
effect outweighs the dilution effect [219]. As the concentration of fibers is
increased to a higher level the tensile properties gradually improve to give strength
higher than that of the matrix. The concentration of fibers beyond which the
properties of the composite improve above the original matrix strength is known as
optimum fiber concentration. In order to achieve improvement in mechanical
properties with short fibers, the matrix is loaded beyond this volume fraction of
fiber. In rubbers this optimum fiber concentration is quite often found to lie
between 25 and 35 phr. This has been observed by several researchers [96,134-135,
220-221] for various natural and synthetic fibers in rubbers. Quite often at
concentration beyond 35 to 40 phr the strength again decreases, because there is
insufficient matrix material to adhere the fibers together.
1.7.6 Fiber- matrix adhesion
Proper reinforcement of rubber matrix using fibers can be achieved only if
there exist adequate adhesion between the fiber and the rubber. The fiber- matrix
adhesion is important in determining the mechanical, dynamic mechanical and
rheological characteristics of the composites since the stress transfer occurs at the
interface from matrix to fiber. In short fiber-rubber composites, after the selection
of suitable fiber and rubber matrix, the next most important parameter is the
achievement of adequate adhesion between the fiber and the matrix.
The fiber- matrix interface adhesion can be explained by five main
mechanisms.
(i)

Adsorption and wetting

This is due to the physical attraction between the surfaces, which is better

understood by considering the wetting of solid surfaces by liquids. Between two

solids, the surface roughness prevents the wetting except at isolated points. When
27

Chapter-1

the fiber surface is contaminated, the effective surface energy decreases. This
hinders a strong physical bond between fiber and matrix interface.
(ii)

Interdiffusion
Polymer molecules can be diffused into the molecular network of the fiber

surface as shown in figure 1.6 a. The bond strength will depend on the amount of
molecular conformation, constituents involved and the ease of molecular motion.

(a)

(b)

________________
_____
___

(c)

(d)

(e)
Figure 1.6. Schematic representations of various fiber matrix adhesions.

28

Introduction

(iii) Electrostatic attraction

This type of linkage is possible when there is a charge difference at the
interface. The electrostatic interaction at the interface is shown in figure 1.6 (b) &
(c). The anionic and cationic species present at the fiber and matrix phases will
have an important role in the bonding of the fiber matrix composites via
electrostatic attraction. Introduction of coupling agents at the interface can enhance
bonding through the attraction of cationic functional groups by anionic surface and
vice versa.
(iv)

Chemical bonding
Chemical bonds can be formed between chemical groups on the fiber surface

and a compatible chemical group in the matrix as shown in figure 1.6 (d). The type
of bond determines the strength. Interfacial chemical bonding can increase the
adhesive bond strength by preventing molecular slippage at a sharp interface during
fracture and by increasing the fracture energy by increasing the interfacial
attraction.
(v)

Mechanical adhesion
Mechanical interlocking at the fiber-matrix interface is possible as given in

figure 1.6 (e). The degree of roughness of the fiber surface is very significant in
determining the mechanical and chemical bonding at the interface. This is due to
the larger surface area available on a rough fiber. Surface roughness can increase
the adhesive bond strength by promoting wetting or providing mechanical
anchoring sites.
Naturally occurring fibers such as cotton, cellulose, etc., have short whiskers
protruding from the surface, which help to give a physical bond when mixed in
rubber. Glass, Nylon, polyester and rayon have smooth surfaces and adhesion of
these fibers to the rubber matrix is comparatively poor. In addition, these synthetic

29

Chapter-1

fibers have chemically unreactive surfaces, which must be treated to enable a bond
to form with the rubber. In general, the fibers are dipped in adhesives in the latex
form and this technology is the most common one used for continuous fibers.
Fiber adhesion to rubber compound is always a field of extensive research
[222-226]. The adhesion between elastomers and fibers was discussed by Kubo
[227]. Hisaki et al. [228] and Kubo [229] proposed a three-layer model composed
of fibers, adhesive agents and elastomers to explain the adhesion between
elastomers and fibers. Effect of adhesive-coated glass fiber in natural rubber (NR),
acrylonitrile butadiene rubber (NBR), and ethylene-propylene-diene rubber
(EPDM) formulations, with respect to the cyclic loading, abrasion, and accelerated
aging was studied by Rathinasamy and coworkers [230]. Sreeja et al. reported the
use of a urethane- based bonding agent for improving fiber-matrix bonding in short
Nylon 6 reinforced NBR and SBR composites [231-232]. Effect of ureathane based
bonding agent on the cure and mechanical properties of short fiber-polyurethane
elastomer composites have been reported by Suhara et al. [233-234]. Effect of
Epoxy based bonding agent on the cure, mechanical, thermal and rheological
properties of short Nylon-6 fiber reinforced NBR, SBR and CR composites have
been studied by Seema et al.[101-102,104,109,123,189].
1.7.6.1 HRH dry bonding system
The dry bonding system commonly used in rubbers is the HRH system
consisting of hydrated silica, resorcinol and hexamethylene tetramine to create
adhesion between fiber and rubber matrix. Compared to adhesive dipping, the use of a
tricomponent dry bonding system is easy. This is because, the constituents of the dry
bonding system can be added to the rubber matrix like any other compounding
ingredients and extra processes like dipping and drying can be avoided. Figure1.7
shows the schematic representation of the enhanced adhesion between Nylon 6 fiber
and natural rubber due to the presence of HRH bonding system [235].

30

Introduction

Figure 1.7. Mechanism of the HRH bonding in Natural Rubber Nylon 6

fiber composites.

The history of dry bonding system dates back to 1967, when Dunnom [236]
observed a marked difference in the adhesion level by adding silica to a compound
containing resorcinol and hexa. Derringer [216], Goettler and Shen [237], Murty
and De [63] and OConnor [195] described the various aspects of short fiber
adhesion to rubber in the presence of the dry bonding system. The use of HRH dry
bonding system in various short fiber-rubber composites was described by several
other authors [13, 84, 141-143, 203]. Setua and De [196] found that in short silk
fiber reinforced nitrile rubber composites, the adhesion between fiber and matrix
was complete only when all the three components of the dry bonding system were

31

Chapter-1

present together. They also reported that a properly bonded fiber-filled matrix
showed good ageing resistance.
Ramayya et al. [238] replaced silica by carbon black in the tricomponent dry
bonding system to study the adhesion between the rayon fiber and natural rubber
and reported that the highest degree of bonding was achieved when silica was
replaced with carbon black. Murty and De [65] made similar observations.
However, Murty et al. [151] observed that the presence of carbon black did not
increase the level of adhesion between short jute fiber and natural rubber. Akthar et
al. [209] reported that although the properties of short silk fiber reinforced
thermoplastic elastomers showed improvement on the addition of the dry bonding
system, the comparatively long cure time required for the full development of
adhesion between the fiber and matrix was the major disadvantage associated with
the incorporation of the bonding system. Suhara et al. [239] reported that in
presence of HRH bonding system, the water liberated during resin formation
caused hydrolysis of urethane linkages and hence HRH system could not be used as
interfacial bonding agent for polyurethane-short polyester fiber composites. Rajeev
et al. [106] studied the effect of dry bonding system in improving the adhesion
between the fiber and matrix of short melamine fiber-nitrile rubber composite.
Rajeev et al [64] also investigated the atomic force microscopy of short melamine
fiber reinforced EPDM rubber composites containing HRH dry bonding system.
To improve the adhesion between fibers and matrix various oxidative and non oxidative chemical treatments are available for natural and synthetic fibers [240-241].
Anthome et al. [242] and Coran et al. [243] have reviewed the reinforcement of
elastomers with various treated short cellulosic fibers and their mechanism of
reinforcement. Several researchers have investigated the use of treated short natural
fibers like jute, coir, sisal, oil palm, bamboo etc. as reinforcing elements for rubber
composites [134-136,203,244-245]. Improvement of interfacial adhesion of poly

32

Introduction

(m-phenylene isophthalamide) short fiber-thermoplastic elastomer composites was

achieved with N-alkylation on fiber surface [246]. The interlaminar shear strength of
rare earth treated aramid fiber reinforced epoxy composites was studied by Wu et al.
[247]. Debasish and co workers [87] investigated the effect of bonding agent on cure
and mechanical properties of alkali treated glass fiber filled natural rubber composites.
A good extent of adhesion is required for high performance short fiber composites. The
main problem with adhesion in short fiber- rubber composites is that it cannot be
measured quantitatively. The adhesion level can be qualitatively assessed from the
shapes of the stress- strain curves and the study of fracture surfaces using scanning
electron microscope techniques. Restricted equilibrium swelling technique can also be
used to evaluate adhesion [248]. But this measurement is inaccurate since the
restriction may be due to the presence of fibers and the adhesion cannot be separated
out. In the case of viscoelastic properties, with the increase of adhesion level a high
shear will be experienced at the interface thereby the mechanical loss associated with it
also increases [249]. At elevated temperature the interface deteriorates and the value
decreases.

1.8

Multicomponent System
The development of composite materials based on two or more different

types of fillers in a single matrix leads to multicomponent system composites with

a great diversity of material properties. The multicomponent system also known as
hybrid composites. The reinforcement may be fibers, particulate fillers or both.
Research has revealed that the behavior of hybrid composites appears to be the
weighted sum of the individual components in which there is a more favorable
balance between the advantages and disadvantages inherent in any composite
material [250]. It is generally accepted that properties of hybrid composites are
controlled by factors such as nature of matrix, nature, length and relative composition
of the reinforcements, fiber matrix interface and hybrid design [251-252]. Sisal and

33

Chapter-1

glass fibers are good examples of hybrid composites possessing very good
combined properties [253]. Due to the superior properties of glass fibers, the
mechanical properties of the hybrid composites increase with increase in the volume
fraction of glass fibers. Thomas et al. [252] have studied the properties of sisal / saw
dust hybrid fiber composites with phenol formaldehyde resin as a function of sisal
fiber loading. It was found that mechanical properties like tensile and flexural
strength increased with sisal fiber content. This is due to the fact that the sisal fiber
possesses moderately higher strength and modulus than saw dust. Mishra et al. [254]
studied the mechanical properties of sisal and pineapple /glass fiber reinforced
polyester composites. They found that the addition of small amount of glass fibers to
the pineapple leaf fiber and sisal fiber reinforced polyester matrix enhanced the
mechanical properties of the resulting hybrid composites. Rozman et al. [255]
studied the tensile and flexural properties of polypropylene / oil palm / glass fiber
hybrid composites and found that incorporation of both fibers into the polypropylene
matrix improved the tensile and flexural strength by the increasing level of overall
fiber loading. Junior et al. [256] used plain weaved hybrid ramie-cotton fibers as
reinforcement for polyester matrix. The tensile behavior was dominated by the
volume fraction of the ramie fibers aligned in the test direction. Cotton fiber had a
minor reinforcement effect. This was due to the weak cotton polyester interface as
well as poor cotton alignment. Hybrid composites containing glass fiber mat and coir
fiber mat in polyester matrix was prepared by Rout et al. [257]. Hybrid composites
containing surface modified coir fibers showed significant improvement in flexural
strength and reduced water absorption. Sreekala et al. [258] prepared high
performance phenol formaldehyde composite reinforced with oil palm and glass
fibers. It has been found that there exists a positive hybrid effect for the flexural
modulus and unnotched impact strength. Natural rubber composite reinforced with
sisal/oil palm, sisal/coir hybrid fibers were prepared by Maya et al. [259] and
Haseena et al. [260] found that the hybridization had a significant effect in improving
34

Introduction

the mechanical properties of the natural rubber composite when compared with the
composite containing individual fibers.
The hybrid composites based on particulate fillers and fibers has also been
studied [261-263]. Synthesis, fabrication, mechanical, electrical, and moisture
absorption study of epoxy polyurethane-jute and epoxy polyurethane-juterice/wheat husk hybrid composites was reported by Mavan et al [264]. Jamal and
co-workers [265] studied the tensile properties of wood flour / kenaf fiber
polypropylene hybrid composites. Study on morphological, rheological, and
mechanical properties of PP/SEBS-MA/SGF hybrid composites was done by
Mohseni et al. [266]. Property optimization in nitrile rubber composites via hybrid
filler systems was reported by Nugay [112]. Rheological behavior of hybrid rubber
nanocomposite was studied by Bandyopadhyay and co workers [267].

1.9

Nanocomposites
Nanocomposites are a new class of composites that are particle-filled

polymers for which at least one dimension of the dispersed particles is in the
nanometer range [268-270]. Nanometer is an atomic dimension and hence the
properties of nanoclusters or parcticles are reflective of atoms rather than bulk
materials. An example for nanocomposite in nature is the natural bone consisting of
approximately 30 % matrix material and 70 % nanosized mineral. Here the matrix
material is collagen fibers (polymer) and the mineral is hydroxyapatite crystals of
50 nm x 25 nm x 3nm size (ceramic). The outstanding reinforcement of
nanocomposite is primarily attributed to the large interfacial area per unit volume
or weight of the dispersed phase. The nanolayers have much higher aspect ratio
than typical microscopic aggregates [268,271-272]. The three major advantages
that nanocomposites have over conventional composites are as follows.

Lighter weight due to low filler loading

Low cost due to fewer amount of filler use

35

Chapter-1

Improved properties such as mechanical, thermal, optical, electrical, barrier

etc., compared with conventional composites at very low loading of filler.

Three types of nanocomposites can be distinguished depending upon the

number of dimensions of the dispersed particles in the nanometer range [268] as
follows

Nanocomposites that can be reinforced by isodimentional nanofillers

which have three dimensions in the nanometer range. Eg:-Spherical silica
nanoparticles obtained by in-situ sol-gel methods [273-274] or by
polymerization promoted directly from their surface [275].

Nanocomposites which can be reinforced by fillers which have only two

dimensions in the nanometer scale. Eg:- Carbon nanotube [276-277] or
cellulose whiskers [278-279 ]

The reinforcing phase, in the shape of platelets, has only one dimension
on a nano level. Eg: - Clays and layered silicates.

Polymer based organic / inorganic nanocomposites have gained increasing

attention in the field of materials science [280-282]. Effect of acrylic polymer and
nanocomposite with nano-SiO2 on thermal degradation and fire resistance of ammonium
polyphosphatedipentaerythritolmelamine (APPDPERMEL) coating was studied by
Zhenyu and co workers [283]. Effect of microstructure of acrylic copolymer / terpolymer
on the properties of silica based nanocomposites prepared by solgel technique was
studied by Patel et al. [284]. Bandyopadhyay et al. [285] studied the reaction
parameters on the structure and properties of acrylic rubber / silica hybrid
nanocomposites prepared by sol-gel technique.

1.10 Silica
Silica, or silicon dioxide, SiO2, in its pure form is colorless to white.
Silica is widely and abundantly distributed throughout the earth, both in the

36

Introduction

pure state and in silicates, (e.g., in quartz, agate, amethyst, chalcedony, flint,
jasper, onyx and rock crystal), opal, sand, sandstone, clay, granite and many
other rocks. Silica occurs in several forms and is insoluble in water, slightly
soluble in alkalies and soluble in dilute hydrofluoric acid. It exists in two
varieties, amorphous and crystalline. In crystalline forms, the structures are
characterized by tetrahedral configuration of atoms within the crystals, whereas
in the amorphous forms, the SiO4 (silicate) subunits show no regular lattice
pattern in the structures. In silicon dioxide, silicon atom uses d orbitals for
bonding and hence SiO2 exists as infinite three-dimensional structures and it is
a high melting solid [286]. Silica which is amorphous contains about 4% water
and can be represented as SiO2.nH2O. It consists of silicon and oxygen arranged
in a tetrahedral structure. Surface silanol concentration (silanol groups Si-OH) influence the degree of hydration. Water content can affect processing and
vulcanization [287]. Absorbed water can decrease cure time, tensile strength
and also abrasion resistance [288]. The hydroxyl groups on the surface of the
silica control surface acidity. This intrinsic acidity can influence vulcanization.
These sites affect the rubber filler interaction. A general silica structure is
depicted in Figure l. 8.

Figure l. 8. Adsorptive nature of silica filler

37

Chapter-1

1.10.1 Silica versus carbon black

Compared to carbon black, silica is characterized by weaker filler-polymer
interactions and stronger filler-filler interactions. This results in a higher compound
viscosity, higher modulus at low strain amplitudes, lower modulus at high strain
amplitudes and lower bound rubber content [289]. However, the silica in
combination with a coupling agent has a higher reinforcing effect and different
dynamic mechanical properties compared to carbon black [290]. When replacing
carbon black by silica combined with a coupling agent the following properties are
influenced predominantly.
Tear, abrasion and heat resistance
Flex stability
Hardness, stiffness and modulus
Tack
Heat build up
Resilience
The stronger reinforcing effect of silica compared to carbon black allows the
reduction of the filler content without any negative influence on the property
profile, but with an additional positive effect on elasticity due to the higher ratio of
elastic component to damping filler. This results in an additional reduction of the
rolling resistance. The stability of the covalent silica - polymer network results in a
lower rate of breaking and reformation of the silica - polymer bonds compared to
the carbon black - polymer network during a deformation cycle, resulting in a
decrease of the loss modulus. A low value of the loss modulus together with a high
value of the storage modulus results in a low value of the phase angle. As both, loss
modulus and storage modulus, depend on deformation, the phase angle is also
influenced by the applied strain, it increases with increasing deformation [288].

38

Introduction

1.10.2 Production and characterization of silica

Acidification of alkali silicate solutions under controlled conditions produces
precipitated silica [291].
Na2SiO3 + 2HCl 2NaCl + H2O + SiO2

........................................(1.7)

Colloidal pyrogenic silica is produced by reaction of silicon tetrachloride at

high temperatures with water.
SiC14 + 2 H2O SiO2 + 4HCl

........................................(1.8)

The reaction products are quenched immediately after coming out of the burner.

Pyrogenic silica is too active and expensive [292]. Precipitated silica is silicon dioxide
containing about 10 - 14% water. They are reinforcing fillers giving composites of
high tensile strength, tear resistance, abrasion resistance and hardness. It is being used
in the manufacture of translucent and coloured products, shoe soling, tyres and other
mechanical rubber goods. Fumed or pyrogenic silica is silicon dioxide containing less
than 2% combined water. These silicas are highly reinforcing fillers of very small
particle size, giving high tensile strength, tear resistance and abrasion resistance
particularly to silicone rubbers [293]. Characterization of silica filler is also based on
particle size and specific surface area. Surface area measurement is usually done by
nitrogen adsorption (BET) method. Also pH, chemical composition and oil absorption
are specified. The smallest physically observable primary particle for precipitated silica
is about 15-20 m and for fumed silica it is about 15 m in size. The surface forces of
the small primary particles are so high that many particles agglomerate to form the socalled secondary particles. Usually the shear forces generated during rubber mixing is
not sufficient enough to disperse primary filler particles in the rubber [292]. The
secondary particles of silica fillers form further agglomerates. They form chain-like
structures, the so-called tertiary structures. Though the tertiary structures are also
relatively stable, they get more or less shattered by the shear forces during mixing
[292]. The higher the shear force, the better the dispersion.
39

Chapter-1

1.10.3 Nanosilica
Nanosilica consists of spherical particles having a diameter less than 100 nm.
Chemically speaking, they are made of silicon and oxygen atoms (Fig.1.9).

Figure 1.9. Chemical structure of nanosilica

Although silica was up to now widely used in polymer formulation as

additives to master the system rheology and enhance mechanical properties of the
polymers, nanosilica throws the door wide open for new applications. Silica
synthesis evolved during last decades from thermal hydrolysis of silane resulting in
not easily dispersible aggregated, nanoparticles to sol-gel process resulting in welldefined nanoparticles highly compatible with the targeted matrix. Processes
enabling chemically tuned and well integrated particles together with the nanoscale
effect are a highway to high performance nanocomposite materials having
enhanced mechanical properties and excellent surface properties.
1.10.3.1 Synthesis of nanosilica

Several methods are used to produce nanosilica from various sources [294299]. A cheap and environment friendly route towards the synthesis of Poly(vinyl
alcohol) / nanosilica hybrid composites has been presented by Tapasi et al. [300].
This is a sol-gel method in which the acid plays a catalytic role in enhancing sol-

40

Introduction

gel condensation of silicon alkoxides within poly (vinyl alcohol). First colloidally
stable silica was prepared by the acid neutralization with an objective to increase
the gelation time and decrease rate of self-condensation of silica. At lower PVA
concentration the silica has a tendency to undergo self-condensation and at higher
PVA concentration, co-condensation occurs.
Nanosilica can be synthesized by precipitation method using sodium silicate
and hydrochloric acid in presence of a polymeric dispersing agent. Poly (vinyl
alcohol), starch and carboxy (methyl cellulose) were found to be good dispersing
agent because they are macromolecules and contain a large number of hydroxyl
groups per molecule.
Dispersing agents used in the synthesis of nanosilica
(a)

Carboxy (methyl cellulose) (CMC)

Carboxy (methyl cellulose) (CMC) is a derivative of cellulose formed by its

reaction with alkali and chloroacetic acid. Sodium carboxy methyl cellulose is an
anionic water soluble polymer. The CMC structure is based on the -(1

4)-D-

glucopyranose polymer of cellulose. Different preparations may have different

degrees of substitution, but it is generally in the range 0.6 - 0.95 derivatives per
monomer unit. CMC molecules are somewhat shorter, on average, than native
cellulose with uneven derivatization giving areas of high and low substitution.

Figure 1.10. Structural unit of Carboxy methyl cellulose

41

Chapter-1

This substitution is mostly 2-O- and 6-O-linked, followed in order of

importance by 2, 6-di-O- then 3-O-, 3, 6-di-O-, 2, 3-di-O- lastly 2, 3, 6-tri-O.linked. It appears that the substitution reaction is a slightly cooperative (within
residues) rather than random process giving slightly higher than expected
unsubstituted and trisubstituted areas. CMC molecules are most extended (rod-like)
at low concentrations but at higher concentrations the molecules overlap and coil
up and then, at high concentrations, entangle to become a thermoreversible gel.
Increasing ionic strength and reducing pH both decrease the viscosity as they cause
the polymer to become more coiled.
(b)

Starch

Starch consists of two types of molecules, amylose (normally 20-30%) and

amylopectin (normally 70-80%). Both consist of polymers of -D-glucose units in
the 4C1 conformation. In amylose these are linked - (1

4)-, with the ring oxygen

atoms all on the same side, whereas in amylopectin about one residue in every
twenty or so is also linked - (1

6) - forming branch-points. The relative

proportions of amylose to amylopectin and - (1

6) - branch-points both depend

on the source of the starch, for example, amylomaizes contain over 50% amylose
whereas 'waxy' maize has almost none (~3%)

Figure 1.11. Structure of amylose

42

Introduction

Figure 1.12. Structure of amylopectin

(c)

Poly (vinyl alcohol)

Poly (vinyl alcohol) is a water-soluble polymer having the following structure:

- (-CH2CH-)OH
It dissolves slowly in cold water, but more rapidly at elevated temperature
and can usually be dissolved completely above 90oC. The aqueous solutions are not
particularly stable especially if traces of acid or base are present. The solutions can
undergo a complex series of reversible and irreversible gelation reactions. For
example, cross-linking can occur at ether linkages, resulting in increased viscosity
through the formation of insoluble products.
1.10.3.2 Applications of nanosilica

Nanosilica can be compounded with rubber and can be used for making
shoe outsoles and rubber foot wear components due to high abrasion
resistance, good grip and non dusting qualities of nanosilica.

43

Chapter-1

Due to their optimal property, nanosilica is used in battery separators.

Nanosilica enhances polymer property like flame retardency, barrier

properties / transparency and scratch resistance

Nanosilica is also used as micro cellular products, like shoes, mat, etc..
due to their foaming control

In opto-electronics nanosilica is used in protective coatings and

encapsulation of electro-optically active materials.

It is used in drug encapsulation; as catalytical vehicles and supports,

preparations, particular calibration standards, chromatography, other
separations and catalysis.

It has been found that silica aero gels coated on surface of granular
activated carbon has four times more ability to remove uranium,
chromium and arsenic from water supplies.

Nano- sized silica abrasives are being researched for use in chemicalmechanical polishing of copper, to minimized mechanical stress during
polishing and reduce defects such as surface scratches, copper peeling,
dishing and erosion.

Nanosilica filled room temperature vulcanized silicone rubber has higher

erosion resistance, lower hydrophilicity and lesser surface roughness and
which is used as insulators in coastal areas

The film of nanosilica known as Xerocoat, when applied to glass / mirror

cuts unwanted reflections from glass, letting more light through, hence
reduces fogging and improves vision.

44

Introduction

1.11 Application of Nanosilica / Short fiber / Elastomeric hybrid Composites

The main application areas for short fiber hybrid composites are hose,
belting, solid tyres and pneumatic tyre components. When continuous cord in rubber
hose is replaced with short fibers, it makes easy processing, economy and higher
production rate. These find applications in the automotive industry as well as for
general purpose utility hoses. Hybrid composite can be utilized as the sole
reinforcement for a moderate performance hose or as auxiliary reinforcement with cord
constructions. They can provide stiffening to soft inner tubes for the application of
metal braids and can extend hose life by bridging the stresses across weaker filaments.
Power transmission belts, more precisely V-belts are the earliest practical application
of rubber fiber composites. A V-belt running over pulleys is subjected to very severe
stresses when bent and flexed at a frequency of thousands of cycles per minute. Tensile
stresses resulting from static tensioning and load transmission are supported by the
reinforcing cord. The compressive side wall pressures are supported mainly by the base
rubber. The ideal material for this part of the V-belt must exhibit high modulus in the
transverse direction and low modulus coupled with high flexibility in the axial
direction. Such complex properties can best be achieved in an anisotropic rubber / short
fiber hybrid composite. Short fibers have the potential for reinforcing low performance
tyres. In automotive and truck tyres they find application in better abrasion resistance
for the chafer strip and in improved cut resistance to treads especially for trucks and
OTR vehicles. In tyre chafing resistance can be improved by adding short fibers to the
surface of the fabric. The apex of radial tyre has been successfully reinforced with
short fibers to give it more stiffness. A small amount of short fibers in the tread of a
truck tyre can reduce the rolling resistance considerably. Sheet roofing can benefit
greatly by the use of short fiber hybrid composites. As short fibers have higher green
strength and cut, tear and puncture resistance, they can be used for sheeting. Seals and
gaskets are potentially large markets for short fiber reinforcement. Short fiber
reinforcement offers excellent creep resistance to seals and gaskets at elevated
45

Chapter-1

temperatures. Chopped Nylon fibers are used to improve the wear of shoe soles. Other
applications are hard roll covers, oil well packing, bearings, diaphragms, dock and ship
fenders etc. Short fibers can reinforce and stiffen rubber in fenders and other impact
applications.

1.12 Scope and Objectives of the Present Work

The concept of nanostructured material design is gaining widespread
importance among the scientific community. The strong reinforcement at low
volume fractions generated tremendous interest in the industry and research circles.
Recent attention has been focused on the suitability of such composites in high
performance application. The concept of short fiber based hybrid nanocomposites
for load bearing applications is fairly new. Property enhancements are expected
due to higher Youngs modulus of the short fibers and fine distribution of
reinforcing nanofillers such as nanosilica, carbon nanotube etc. The studies so far
reported proved that utilization of short fibers as reinforcement in polymer
composites offer economical, environmental and qualitative advantages. By
incorporating particulate nano filler along with short fibers, high performance
hybrid composite can be prepared. They may find application in automotives,
belts, hoses and building industry. However, elastomeric hybrid composites based
on short fiber and nanofiller have not been subjected to a systematic evaluation.
With the growing demand of nanosilica, economic competition and
ecological pressure, there is an increasing need to synthesis nanosilica from a cost
effective source and by a cheap method. The addition of nanofillers to rubbers can
bring about dramatic changes in the properties of rubbers.

The concept of

condensation of silica particle into a dispersed polymeric matrix by the catalytic

action of an acid was adopted from the work of Kotoky and Dolui [300]. Since the
desired product was silica and not the polymer / silica nanocomposite the polymer
concentration was kept low. It was expected that the precipitated silica would be

46

Introduction

collected in the polymer matrix and hence its agglomeration would be prevented.
The addition of the dispersing agent would produce a matrix into which
synthesized silica would be incorporated, thus producing silica in the nanoscale.
The interaction between the hydroxyl groups of dispersing agent and the hydroxyl
groups of silica would result in co-condensation. The synthesized silica after
complete drying is to be calcined to remove the dispersing matrix and to obtain
pure silica. The presence of organic molecule eliminate the need for the usage of
coupling agent during nanocomposite preparation
The use of short fibers as reinforcing agents in elastomers opens up a new
avenue for the utilization of waste fibers, available in plenty from fiber and textile
industries. Recently, short fibers have found a variety of applications in rubbers due to
the ease of mixing and consequent processing advantages in fabricating products of
complicated design coupled with greater reinforcement. The properties of short- fiber
containing composites depend critically on fiber content, orientation and fiber - matrix
interface bond strength. A detailed study of the effect of these parameters on the
composite properties will be highly informative. A strong interfacial bond can
effectively transfer load from the matrix to the fiber and hence can improve the overall
performance of the composite. The interfacial bond is usually strengthened by using
bonding agents. HRH based bonding agent is widely used. The role of silica in HRH
bonding system is to increase the wettability of fibers. Lower the particle size higher
the surface area. Hence nanosilica can be more effective in improving the wettability of
fibers. The use of nanosilica in HRH bonding system can improve adhesion between
the fiber and the matrix. SEM studies provide idea about the interface.
Hybridization is commonly used for improving the properties and for
lowering the cost of conventional composites. It is generally accepted that
properties of hybrid composites are controlled by factors such as nature of matrix,
nature, length and relative composition of the reinforcements, fiber matrix interface

47

Chapter-1

and hybrid design. The hybrid composites based on nanofillers and fibers need to
be studied in detail. The service requirements of the elatomers in different areas of
application are so wide that NR alone can not meet all of them. Of the many
synthetic rubbers being used currently, SBR, NBR and CR find major applications.
The performances of these hybrid composites can be evaluated by studying their
physical and mechanical properties.
Knowledge of the degradation characteristics of the composites is important
in many applications. The thermal stability of the hybrid composite may be
influenced by the presence of short fibers and nanosilica. Thermogravimetry can be
used to study the thermal degradation behavior of the composites.
Fiber matrix interaction in composites can be studied in detail based on the
response of the material to dynamic strains. The nature of the modulus curves is likely
to be a good indication of the fiber- matrix interaction and the nature of the interface.
The main objectives of the present work are summarized as follows:

To synthesize nanosilica from cheap source such as sodium silicate and

make the process less expensive.

To improve the interfacial adhesion between short Nylon fiber and

different rubber matrices

To compare the performance of nanosilica and commercial silica in NR

compounds.

To evaluate the effect of nanosilica as reinforcing filler in Nylon 6 short

fiber hybrid composites based on NR, SBR, NBR and CR .

48

To study the viscoelastic properties of the hybrid composites.

To study the thermal degradation behavior of the hybrid composites.

Introduction

1.13 References
[1]

Lubin , Hand book of composites, Van Nostarnd, New York, 1982.

[2]

Encyclopedia of Polymer Science Engineering, H.F. Mark Edition,JohnWiley

and Sons, New York ,1985

[3]

Nielsen L.E., Fields, J.E., U.S. 3652491 (march28,1972).

[4]

Woods D.W., Ward I.M., J. Mater. Sci. 1994, 29, 2572.

[5]

Sohn M.S., Hu X.Z., Kim J.K., Polym. Polym. Compos. 2001, 9,157.

[6]

Pigott M.R., J. comps. Mater. 1994, 28,588.

[7]

Hiley M.J., Plast.Rubber, Compos. 1999, 28, 210.

[8]

Rajeev R. S., Anil K. Bhowmick,. De S. K Bandyopadhyay S J. Appl.

Polym. Sci., 2003, 90, 544.

[9]

Tjong S.C., Meng Y.Z., J. Appl. Polym. Sci, 1999, 72, 501.

[10]

Gonzalez P.I.,Yong R.J., J.Mater. Sci., 1998, 33, 5715.

[11]

Raghavan J., Wool R. P., J. Appl. Polym. Sci., 1999, 71, 775.

[12]

Sapua S.M., Leenie A., Harimi, M Beng Y.K., Materials and Design, 2006,
27, 689.

[13]

Bipinbal P. K., Kutty S. K. N J. Appl. Polym. Sci. 2008, 109, 1484

[14]

Sreekumar P.A., Pradeesh Albert, Unnikrishnan G., Kuruvilla Joseph, Sabu

Thomas J. Appl. Polym. Sci. 2008, 109, 1547.

[15]

Mondadori N. M. L., Nunes R. C. R., Zattera A. J.,Oliveira R. V. B., Canto

L. B., J. Appl. Polym. Sci. 2008, 109, 3266.

[16]

Qin X. H.,. Xiao B. L . Dong S. M . Jiang D. L, J. Mater. Sci. 2007, 42, 168.

[17]

Amirhossein Esfandiari, Fibers and Polymers, 2008, 9, 234.

[18]

Shan Jin, Yuansuo Zheng, Guoxin Gao, Zhihao Jin, Mater. Sci. Eng. 2008,
483, 322.

[19]

Leaity M.A., Smith P.A., Curtis P.T., Composites, 1992, 23: 387.

[20]

Tiesong Lin, Dechang Jia, Peigang He, Meirong Wang, Defu Liang Mater. Sci.
Eng. 2008, 497, 181.
49

Chapter-1
[21]

Mukherjee M., Das C.K., Kharitonov A.P., Banik K., Mennig G., Chung T.N.
Mater. Sci. Eng. 2006, 441,206.

[22]

Yuanxin Zhou, Mallick, P.K., Mater. Sci. Eng. 2005,393, 303.

[23]

Praveen S., Chakraborty B. Cjayendran S., Raut R. D., Chattopadhyay S. J.

Appl. Polym. Sci., 2009,111,264.

[24]

Mohseni Garakani M., Arefazar A., Nazockdast, H., J. Appl. Polym. Sci.,
2007,104, 2704.

[25]

Atsushi Kato, Shinzo Kohjiya, Yuko Ikeda, Rubber Chem. Technol., 2007,
80,690.

[26]

Ashby M. F. Philosophical Transactions of the Royal Society of London, 1987,

A322: 393.

[27]

Business Communications Co, Inc, Composites: Resins, Fillers, Reinforcements,

Natural Fibers and Nanocomposites (report number RP-178).

[28]

Richardson T., Composites-a design guide, Industrial Press Inc.,200 Madison

Avenue,Newyork, 1987.

[29]

Warner S.B., Fibre Science., Prentice Hall, Engle wood Cliffs, New Jersey, 1995.

[30]

Mallick P.K., Fibre reinforced composite materials, manufacturing and design.,

Marcel Dekker, Inc., Newyork, 1988, Ch. 1., p.18.

[31]

Rogers J.W., Rubber World, 1981, 27, 183.

[32]

Goettler l.A., Lambright A.J.,Leib R.I., Rubber Chem. Technol., 1981, 54: 277.

[33]

Abrate S., Rubber Chem. Technol, 1986, 59, 384.

[34]

Chakraborthy S.K., Setua D.K., De S.K., Rubber Chem. Technol., 1982, 55, 1286.

[35]

Moghe S.R., Rubber Chem. Technol, 1974, 47, 1074.

[36]

Vincent J.F.V, Appl. Comp. Mater. 2000, 7, 269.

[37]

Collier A.T., U.S.1000781, August 15, 1911.

[38]

Ibarra L., J. Appl. Polym. Sci., 1991, 43, 1805.

[39]

Ibarra L., J Appl. Polym. Sci., 1994, 54, 1721.

[40]

Pecorini T.J., Hertzberg R.W., Polym. Compos.1994, 15, 174.

50

Introduction

[41]

Ibarra L., Kautsh. Gum. Kunstst. 1994, 47, 578.

[42]

Ibarra L., Kautsh. Gum. Kunstst. 1995, 48, 860.

[43]

Subramanian V., Seshadri K.R., Ganapathy S., Rubber India, 1997, 49, 9.

[44]

Nunes R.C.R., Affonso J.E.S., Kautsh. Gum. Kunstst, 1999, 52, 787.

[45]

Bhagavan S.S. Tripathy D.K., De S.K. J Appl. Polym. Sci. 1987, 33, 1623.

[46]

Setua D.K., De S.K., J. Mater. Sci. 1985, 20, 2653.

[47]

Bishai A.M., Ghoneim A.M., Ward A.A., Younan A.F. Int. J. Polymer.
Mater. 2002, 51, 793.

[48]

Sreeja T.D., Kutty S.K.N., J. Elastomers Plast., 2001,33, 225.

[49]

Kumar, R., Prasantha. Thomas, S., Sci. Eng. Compos. Mater. 1999, 8, 311.

[50]

Correa R.A., Nunes R.C.R., Franco Filho., Polym. Compos. 1998, 19, 152.

[51]

Mingtao Run, Hongzan Song, Chenguang Yao, Yingjin Wang J Appl. Polym.
Sci.,2007,106, 868.

[52]

Mondadori N. M. L, Nunes R. C. R., Zattera A. J., Oliveira R. V. B., Canto

L. B, J Appl. Polym. Sci., 2008, 109, 3266.

[53]

Das J.N., Nair N.G., Subramanian S., Plast. Rubber Compos. Process. Appl.
1993, 20, 249.

[54]

Zuev Yu.S., Kauch Rezina, 1991, 12, 30.

[55]

Maya J.J., Rajesh D., Anandjiwala,

Interfaces, 2007, 14, 733.

[56]

Thomas N. Abraham, George K.E. Polym. Plast. Technol. Eng. 2007, 46, 321.

[57]

Anuar H, Ahmad S. H., Rasid R, Nik Daud N. S., Polym. Plast. Technol.
Eng.2006, 45, 1059.

[58]

Kun Byung Kyu, Park Chen Young, Shen Kwi Sook, Komu Hakhoechi, 1991,
26, 246.

[59]

Zhou Yanhao, Zhang Liqun, Li Chen, Hecheng Xiangjio Gongye, 1998, 21, 1.

[60]

Kadowaki, Kazunori Kilajima, Tan Michio, Jpn. Kokai Tokkyo Koho JP

09,320,368 (97,320,368) 12 Dec. 1997.

Pothan L.A. Thomas S., Compos.

51

Chapter-1
[61]

Wazzan A.A. Int. J. Polymer. Mater. 2004, 53, 59.

[62]

Geethamma V.G., Kalaprasad G. Gabriel G.Thomas S. Compos.Part.A,

2005, 36, 1499.

[63]

Murty V.M., De S.K., Polym. Eng. Revs. 1984, 4, 313.

[64]

Rajeev R.S., De S.K., Bhowmic A.K., J. Mater. Sci. 2001, 36, 2621.

[65]

Murty V.M., De S.K, J Appl. Polym. Sci., 1982, 27, 4611.

[66]

Chakraborty S.K., Setua D.K., De S.K., Rubber Chem. Technol., 1982, 55, 1286.

[67]

Rajesh c., Unnikrishnan G., Purushothaman E., Sabu T., J Appl. Polym. Sci.,
2004, 92, 1023.

[68]

Geethamma V.G., Reethamma J., Thomas S., J Appl. Polym. Sci. 1995, 55, 583.

[69]

Geethamma V.G., Thomas M.K., Lakshminarayanan R., Thamas S., Polymer,

1998, 39, 6.

[70]

Kutty S.K.N., Nando G.B. Plast.Rub. Comp., 1993, 19, 105.

[71]

Kutty S.K.N., De P.P., Nando G.B., Plast. Rubber Process. Appl., 1990, 14, 109.

[72]

Sreekala M.S., Kumaran M.G., Joseph S., Jacob M., Thomas S, Appl.
Compos. Mater. 2000, 7, 295.

[73]

Cao Y., Shibata S., Fukumoto I., Composites Part A, 2006, 37, 423.

[74]

Idicula M., Neelakantan N.R., Oommen Z., Joseph K., Thomas S., J Appl.
Polym. Sci. 2005, 96, 1699.

[75]

Sreekala M.S., Thomas S., Polym. Compos. , 2005, 26, 388.

[76]

Weyenberg V., Chi Truong T., Vangrimde, B., Verpoest I., Composites Part A,
2006, 37, 1368.

[77]

Toriz G., Arvidsson R., Westin M.,Gatenholm P., J Appl. Polym. Sci. 2003,
88, 337.

[78]

Wong S., Shanks R., Hodzic A.,Macromol. Mater.Engg. 2002, 287, 647.

[79]

Melo J.D.D., Radford D.W. J. Compos. Mater. 2003, 37, 129.

[80]

Afaghi Khatibi A, Mai Y.W., Composites Part A.,2002, 33, 129.

[81]

Amash A., Hildebrandt F.I., Zugenmaier, Polymer., 2002, 5, 385.

52

Introduction

[82]

Pothen L.A., Thomas S., Compos. Sci. Technol., 2003, 63, 1231.

[83]

Pothen L.A., Thomas S. J. Appl. Polym. Sci.. 2004, 91, 3856.

[84]

Zhang Zhicheng, Zheng Yuansuo., Xiandai Huagong 2002, 22, 38.

[85]

Suhara F., Kutty S.K.N., Nando G.B. Polym. Plast. Technol. Eng., 1997, 36, 399.

[86]

Suhara F., Kutty S.K.N., Nando G.B., Bhattacharya A.K., Polym. Plast.
Technol. Eng., 1998, 37, 57.

[87]

Suhara F., Kutty S.K.N., Nando G.B. Polym.Degrad. Stab., 1998, 61, 9.

[88]

Kohjiya S., Ikeda Y., J. Sol-Gel Sci. Technol. 2003, 26, 495.

[89]

Abdelmouleh M.,Belgacem M.N.,Dufresne A., Compos. Sci. Technol., 2007,

67, 1627.

[90]

Debasish De, Debapriya De, Basudam A., J Appl. Polym. Sci. 2006, 101,
3151.

[91]

Atsushi Kato, Shinzo Kohjiya, Yuko Ikeda, Rubber Chem. Technol., 2007,
80, 690.

[92]

Yoshitaka Uchiyama, Noriaki Wada, Tomoaki Iwai, Seiichi Ueda, Shinji Sado,
J Appl. Polym. Sci., 2005, 95, 82.

[93]

George J., Joseph K., Bhagavan S.S., Thomas S.,Mater.,Lett., 1993, 18, 163.

[94]

Varghese S., Kuriakose B., Thomas S., Plast. Rubb.Comp. Proc.Appl., 1993,
20, 930.

[95]

Varghese S., Kuriakose B., Thomas S, Koshy A.T.,Ind. J. Nat. rubber, 1991, 4, 55.

[96]

Varghese S., Kuriakose B., Thomas S, Koshy A.T, J.Adhes.Sci.Technol.,1994,

8, 235.

[97]

Varghese S., Kuriakose B., Thomas S., Rubber Chem. Technol.,1997, 68,75.

[98]

Maiti M Sadhu S., Bhowmick A.K., J. Appl. Polym. Sci., 2005, 96, 443.

[99]

Ansarifar A.,Wang
2006,79, 39.

[100]

Prasantha Kumar, R., Thomas S., J.Adhes.Sci.Technol., 2001, 15, 33.

[101]

Seema A., Kutty S.K.N., Int. J. Polymer. Mater., 2006, 55, 25.

L.,Ellis

R.J.,Kirtley S.P., Rubber Chem. Technol.,

53

Chapter-1
[102]

Seema A., Kutty S.K.N., Int. J. Polymer. Mater., 2005, 54, 1031.

[103]

Werner Hofman, In: Rubber Technology Handbook' -Ed. Werner Hofmann,

Hanser Publishers, Munich, 1989, Chapter 4, 284.

[104]

Seema A., Kutty S.K.N., Int. J. Polym. Anal. Charact. 2005, 10, 169.

[105]

Susmita S., Bhowmick A.K. J.Polym.Sci., 2005, 43, 1854.

[106]

Rajeev R.S., De S.K., Bhowmic A.K., Bandyopadhyay S. J. Appl. Polym.

Sci., 2003, 90, 544.

[107]

Ono Yoshiki, Tamino Kichiya, Nippon Gomu Kyokaishi, 1992, 19,109.

[108]

Sreeja T. D., Kutty S. K. N., J.Elastomers Plast. 2002, 34,157

[109]

Seema A., Kutty S. K. N., J. Appl. Polym. Sci., 2006, 99, 532

[110]

Rajeev R.S., De. S.K., Bhowmick A. K., Baby J., Polym. Degrad. Stab. ;
2003, 79, 449.

[111]

Wang M.J.,Wolff S., Donnet J.B., Rubber Chem.Technol., 1991, 64, 559.

[112]

Nugay N., Erman B., J. Appl. Polym. Sci., 2001, 79, 366.

[113]

Seema A., Kutty S. K. N., Polym. Plast. Technol. Eng., 2005, 44, 1139.

[114]

Jana P.B., De S.K., Plast. Rubber Compos. Process. Appl., 1992, 17, 43.

[115]

Setua D.K., De S.K., Rubber Chem. Technol., 1984, 29, 3097.

[116]

Park Chan., Kim, Byung Kyu., Pollimo., 1989, 13, 882.

[117]

Silva V. P., Gonalves M. C, Yoshida I. V. P. J. Appl. Polym. Sci., 2006, 101, 290.

[118]

Kozlov G. V., Burya A. I., Zaikov G. E. . J. Appl. Polym. Sci., 2006, 100, 2821.

[119]

Hong Gun Kim, J. Mecha. Sci. Technol. , 2008, 22, 236.

[120]

Rahman K.A., Hepburn C., Eur. Rubber J, 1981, 10, 7.

[121]

Rueda L.I., Anton C.C., Rodriguez M.C.T., Polym. Compos., 1988, 9, 198.

[122]

Moghe S.R., Rubber world, 1983, 187, 16.

[123]

Gassan J., Dietz T., Bledzki A.K., Compos. Interfaces, 2000, 7, 103.

[124]

Mothe C.G., Araujo C.R., Thermochin, Acta, 2000, 321, 357.

54

Introduction

[125]

Boustany K., Arnold R.L., J.Elastomers Plast., 1976, 82, 160.

[126]

Das N.C., Chaki T.K., Khastgir J. Polym. Eng., 2002, 22,115.

[127]

Zhang B.L., Chen M., Liu H.L., J.Rubber Res., 2001, 4, 82.

[128]

Zebarjrd S.M., Baghari R., Lazzeri A., Plast.Rubber Compos., 2001, 30, 370.

[129]

Arroyo M., Bell M., J. Appl. Polym. Sci., 2002, 83, 2474.

[130]

Sreeja T. D., Kutty S. K. N., Polym. Plast. Technol. Eng., 2002, 41, 77.

[131]

Sreeja T. D., Kutty S. K. N., Polym. Plast. Technol. Eng., 2003, 42, 239.

[132]

Nielsen L.E., Mechanical properties of Polymers and composites, Vol 1.

Marcel Dekker, 1974.

[133]

Cook J.G., Hand book of Textile fibres and Natural fibres, 4th Edn.Morrow
Publishing, England.1968.

[134]

Arumugham N., Tamaraselvy K., J Appl Polym Sci., 1989, 37, 2645.

[135]

Ismail H., Edyham M.R., Wirjosentono B., Polymer Testing, 2002, 21, 139.

[136]

Murthy V.M., De S.K., J Appl Polym Sci, 1984, 29, 1355.

[137]

Ismail H., Rozman H.D., Ishiaku U.S., Polym International, 1997, 43, 23.

[138]

Flink P., Stenberg B., Br.Polym. J., 1990, 22,193.

[139]

Ahlblad G., Reitberger T., Stenberg B., Danielson Polym.Int., 1996, 39, 261.

[140]

Setua D.K., De S.K., J.Mater. Sci., 1984, 29, 3097.

[141]

Murthy V.M., De S.K., Rubber Chem. Technol., 1982, 55, 287.

[142]

Setua D.K., De S.K., Rubber Chem. Technol., 1983, 56, 808.

[143]

Chakraborty S.K., Setua D.K., De S.K., Rubber Chem. Technol., 1982, 55, 1286.

[144]

Bhattacharyya T.B., Biswas A.K., Chatterjee J., Pramanick D., Plast. Rubber
Process. Appl., 1986, 6, 119.

[145]

Arumugam N., Selvy K.T., Rao K.V., Rajalingam P., J Appl. Polym. Sci.,
1989, 37, 2645.

[146]

Czarnecki L.,White J.L., J Appl. Polym. Sci.., 1980, 25, 1217.

55

Chapter-1
[147]

Cubberly R.H., Hartmann W.R., U.S.2564882 August 21, 1951.

[148]

Waterman R.R., Morris D.C., U.S. 3305509, February 21, 1967.

[149]

Gregg R.A., Rubber Chem. Technol., 1972, 45, 49.

[150]

Marzocchi A., S. African Patent No. ZA 6805086, June3, 1969.

[151]

Murthy V.M., De S.K., Bhagavan S.S, Sivaramakrishnan R., Athithan S.K.,

J. Appl. Polym. Sci., 1983, 28, 3485.

[152]

Murthy V.M., De S.K., Bhowmick A.K., J. Mater. Sci., 1982, 17, 709.

[153]

Oh J.S., Joo Y.L., Polym. Recycl., 1998, 3, 119.

[154]

Yagi K., Kanoo T., Inada Eur. Pat. No. EP 296613, December 28, 1988.

[155]

Jana P.B., Chaudhury S., Pal A.K., De S.K., Rubber Chem. Technol., 1993, 65, 7.

[156]

Jana P.B., De S.K., Mallick A.K., J. Mater. Sci., 1993, 28, 2097.

[157]

Das N.C., Chaki T.K., Khastgir Chakrabarty A., J ApplPolym Sci., 2001, 80, 1601.

[158]

Das N.C., Chaki T.K., Khastgir Carbon, 2002, 40, 807.

[159]

Pramanik P.K., Khastgir De S.K., Saha T.N., J. Mater. Sci., 1990, 25, 3848.

[160]

Pramanik P.K., Khastgir Saha T.N., J. Mater. Sci., 1993, 28, 3539.

[161]

Correa R.A., Nunes R.C.R., Franco F.W.Z., Polym. Compos. 1998, 19, 152.

[162]

Roy D., Bhowmic A.K., De S.K., Polym. Eng. Sci.,1992,32, 971.

[163]

Roy D., Gupta B.R., J Appl. Polym. Sci., 1993, 49, 1475.

[164]

Roy D., Gupta B.R., Bhattacharya A.K., J.Elastomers Plast., 1993, 25, 46.

[165]

Shonaike G.O., Matsuo T.,J. Reinf. Plast. Compos., 1997, 16, 217.

[166]

Ibarra L., Macias A., Palma E., Kautsch. Gumm. Kunstst., 1995, 48, 180.

[167]

Ibarra L., Macias A., Palma E., J Appl. Polym. Sci., 1996, 61, 2447.

[168]

Abdul-Aziz, M.M., Youssef H.A., Miligy A.A., Yoshii F., Makuuchi K.,
Polym. Polym. Compos. 1996, 4, 259.

[169]

Older D.G., Kumar S., UK. Pat.No. GB 2191115, December 8, 1996.

56

Introduction

[170]

Verthe J.J.A., Hubbell J.K., Martin G.M., Can. Pat. No.Ca 2158003, December
8, 1996.

[171]

Gabara V., in Synthetic Fiber MaterialsH. Brody, Ed.,Longman, Harlow,

UK, 1994, p-239.

[172]

Kutty S.K.N., De P.P., Nando G.B., Plast. Rubber Process. Appl., 1993, 15, 23.

[173]

Kutty S.K.N., Nando G.B., J.Adhes.Sci.Technol. 1993, 7, 105.

[174]

Kutty S.K.N., Nando G.B., J. Fire Sci., 1993, 11, 66.

[175]

Weening, Kautsch. Gumm. Kunstst, 1984, 37, 379.

[176]

Andreopoulos A.G., Konstantinidou A.V., Petsales H.J., J Appl. Polym. Sci.,

1990, 38, 2073.

[177]

Susan S., Taweechai A., Wiriya M., Sauvarop B.L., Polymer, 1999, 40, 6437.

[178]

Senapati A.K, Nando G.B., Pradhan B., Int. J. Polym. Mater. 1988, 12, 73.

[179]

Sreeja T. D., Kutty S. K. N., Int. J. Polym. Mater., 2003,52, 239.

[180]

Chen Li, Liu Bo, Zhou Yanhao, Fuhe Cailiao Xuebao, 1989, 6, 79.

[181]

King Chang Kee, Shin Gui Sook, Kim Byung Kyu, Pollimo, 1990, 14, 456.

[182]

Ye L, Pan J, Li D, Jixie Gong Cheng Xuebao, 1990, 26, 68.

[183]

Zhou Yanhao, Chen Tao, Li Chen, Li Donghong, Zhang, L., Heecheng

Xiangjiao Gongye, 1992, 15(6), 329.

[184]

Zhou Yanhao, Chen Tao, Li Chen, Li Donghong,., Heecheng Xiangjiao

Gongye, 1992, 15(2), 294.

[185]

Zhou Y.H., Chen Tao, Li Chen, Li Donghong, Zhang, L, Macromol. Rep.,

1993, 30, 365.

[186]

Bhattacharya J.K., Rubber India, 1994, 46, 36.

[187]

Ma Peiyu, Zhao Jan, Tang J., Dai, G., guofenzi Cailiao Kexue Yu
Gongcheng, 1994, 10, 55.

[188]

Zhang Liqun, Zhou Yanhao, Chen Tao, Li Chen, Li Donghong

Gongye, 1994, 41, 267.

[189]

Seema A., Kutty S. K. N., Int. J. Polym. Mater. 2005, 54, 933.

Xiangjiao

57

Chapter-1
[190]

Bhagwan D.A., Lawrence J. B.,Analysis and performance of

composites John Wiley & sons, New York, 1980, cha.-2, p- 21.

[191]

Broutman L.J., Aggarwal B.D., Analysis and performance of fiber

composites, Soc.Plast. Ind., John Wiley and Sons,Newyork ., 1980.

[192]

Monette L., Anderson M.P., Grest G.S., Polym. Comp., 1993, 14, 101.

[193]

Termonia Y., J. Mater. Sci. Lett., 1993, 12, 732.

[194]

Rosen B.W., Fibre Composite Materials, American Society for metals, Metal
Park, Ohio, 1965.

[195]

OConnor J.E., Rubber. Chem. Technol., 1977, 50, 945.

[196]

Setua D.K., De S.K., J. Mater. Sci., 1984, 19, 983.

[197]

Kutty S.K.N., Nando G.B., Int. J.Polym. Mater.1992, 17, 235.

[198]

Noguchi., Ashida M., Mashimo S., Nippon Gomu Kyokaishi, 1984, 12, 829.

[199]

Kutty S.K.N, Nando G.B, J. Appl. Polym. Sci., 1991, 43, 1913.

[200]

OConnar J.E., Rubb. Chem. Technol., 1974, 47, 396.

[201]

Boustany K., Arnold R. L., J. Elasto. Plast., 1976, 8, 160.

[202]

Boustany K., Coran A.Y., US Patent No. 3 397 364 ,to Monsanto C, 1972.

[203]

Murthy V.M., De S.K., J. Appl. Polym. Sci., 1984, 29, 1355.

[204]

Ibarra L., Chamorro A.C., J. Appl. Polym. Sci., 1991, 43, 1805.

[205]

Rueda L.I., Chamorro A.C., J. Appl. Polym. Sci., 1989, 37, 1197.

[206]

Hong Gun Kim, J. Mech. Sci. Technol., 2008, 22, 130.

[207]

David A. Norman, Richard E. Robertson, J. Appl. Polym. Sci., 2003, 90, 2740.

[208]

Kozlov G. V., Burya A. I., Zaikov G. E., J. Appl. Polym. Sci., 2006, 100, 2821.

[209]

Akthar S.,De P.P., De S.K., J. Appl. Polym. Sci., 1986, 32, 5123.

[210]

Goettler L.A., Lambright A.J.,Leib R.I., Rubb Chem Technol , 1979, 52, 838.

[211]

Varghese S.,Kuriakose B., Thomas S., Ind. J. Nat. rubber, 1992, 5, 18.

[212]

Joseph K., Thomas S., mater. Lett., 1992, 15, 224.

58

fiber

Introduction

[213]

Senapati A.K, Kutty S.K.N., Nando G.B. Pradhan B.,Int. J. Polym. Mater.
1989, 12, 203

[214]

Dunnom D.D., Wagner M.P., Derringer G.C., Chemical Division, PPG

Industries Inc., US Patent No.3746669, 1973.

[215]

Derriger D.C., Rubber World, 1971, 45, 165.

[216]

Derriger D.C., J. Elastoplast., 1971, 3, 230.

[217]

Prasanth Kumar R., Thomas S., J. Appl. Polym. Sci., 1995, 58, 597.

[218]

Senapati A.K., Nando G.B., Int. J.Polym. Mater., 1988, 12, 73.

[219]

Kutty S.K.N., Nando G.B., J. Appl. Poym. Sci., 1991, 43, 1913.

[220]

Geethamma V.G., Thomas S., Int. J. Polym. Mater., 1996, 32, 147.

[221]

Prasanth Kumar R., Thomas S., Bull. Mater. Sci., 1995, 18, 1021.

[222]

Wennekes W. B. Datta R. N., Noordermeer J.W.M., Elkink F. Rubber.

Chem. Technol., 2008, 81, 523.

[223]

Wennekes W. B. Datta R. N., Noordermeer J.W.M.,. Rubber Chem. Technol.,

2007, 80, 545.

[224]

Wennekes W. B. Datta R. N., Noordermeer J.W.M., Rubber Chem. Technol.,

2007, 80, 565.

[225]

Datta R., Teijin Twaron B.V., Rubber Chem.Technol., 2007, 80, 296.

[226]

Yan Li; Yiu-Wing Mai, J. Adhesion, 2006, 82, 527.

[227]

Kubo Y., in Elastomer Technology Hand bookN.P. Cheremisinoff, Ed., CRC

Press, Boca Raton, 1993, p-857.

[228]

Hasaki H., Mori O., J. Sci. Rubber ind. Jpn. 1991, 64, 33.

[229]

Kubo Y., Rubber Chem.Technol., 2007, 80, 545.

[230]

Rathinasamy P., Balamurugan P., Balu S., Subrahmanian V. J. Appl.

Polym. Sci., 2004, 91, 1124.

[231]

Sreeja T. D., Kutty S. K. N., Prog. In Rubber Plast. & Recyling Technol. 2002,
18, 283.

[232]

Sreeja T. D., Kutty S. K. N., Advances in Polymer Technology, 2001, 20, 281.

59

Chapter-1
[233]

Suhara F., Kutty S.K.N., Nando G.B., Polym. Plast. Technol. Eng., 1998, 37, 241.

[234]

Suhara F., Kutty S.K.N., Nando G.B, Int. J.Polym. Mater.,1997, 38, 205.

[235]

Blackley D.C., Polymer Lattices, Chapman & hall Publishers, London, Second
Ed. 1997, 3, 515.

[236]

Dunnom D.D., Hi-Sil Bulletin (PPG Ind. Inc.) No. 35, 1967.

[237]

Goettler L.A., Shen S.K., Rubber Chem Technol, 1983, 56, 619.

[238]

Ramayya A.P., Chakraborty S.K., De S.K., J. Appl. Poym. Sci.,1984, 29, 1911.

[239]

Suhara F., Kutty S.K.N., Nando G.B., Plast. Rub. Comp. Proces. Appl. 1995,
24, 37.

[240]

Chawla K.K., Composite Materials, Spriger Verlarg, Newyork, 1987.

[241]

Richardson M.O.W., Polymer Engineering composites, Applied Science

Publishers, London. 1977, p. 1

[242]

Anthonie G., Arnol R.L., Boustany K., Eur. Rubb. J., 1975, 157, 28.

[243]

Hamed P., Coran A.Y., Additives for Plastics, Seymour, Edn. Academic
Press, Newyork., 1982.

[244]

Varghese S., Kuriakose B., Thomas S., Rubber. Chem. Technol., 1997, 63, 550.

[245]

Geethamma V.G., Joseph R. Thomas S., Polymer, 1998, 39, 1483.

[246]

Anongnuch Chantaratcharoen, Chakrit Sirisinha, Taweechai Amornsakchai,

Sauvarop Bualek-Limcharoen, Wiriya, Meesiri. , J. Appl. Poym. Sci., 1999,
74, 2414.

[247]

Wu J. Cheng, X., J. Mater. Sci., 2005, 40, 86.

[248]

Das B., J. Appl. Poym. Sci., 1973, 17, 1019.

[249]

Geethamma V.G., Kalaprasad, G.,Gabriel Groeninckx., Thomas S composites,

Part. A, 2005, 36, 1499.

[250]

Hartikainen J., Hine P., Friedrich K., Comp. Sci. Technol., 2005, 65, 257.

[251]

Idicula M., Neelakandan N.R., Thomas S., Oommen S., Joseph K., J. Appl.
Polym. Sci., 2005, 96, 1699.

[252]

Idicula M., Malhotra S.k., Thomas S., Comp. Sci. Technol., 2005, 65, 106.

60

Introduction

[253]

Kalaprasad G., Joseph K., Thomas S., J. Comp. Mater., 1997, 31, 509.

[254]

Mishra S., Comp. Sci. Technol., 2003, 63, 1377.

[255]

Rozman H.D., Ismail H., Euro. Polym. J., 2001, 37, 1283.

[256]

Junior C.Z.P., Fonseca V.M., Monteiro S.N., Polymer Testing, 2004, 23, 131.

[257]

Rout J., Misra M., Tripathy S.S., Mohanty A.K., Comp. Sci. Technol., 2001,
61,1303.

[258]

Sreekala M.S., Neelakandan N.R., Thomas S., J. Polym. Eng., 1997, 16, 265.

[259]

Maya Jacob, Varghese K.T., Comp. Sci. Technol., 2004, 64, 955.

[260]

Haseena A.P., Unnikrishnan G., Thomas S., Comp. Interf., 2004, 11, 489.

[261]

Ahmed Rehab, Ahmed Akelah, Tarek Agag, Mohamed Betiha, J. Appl. Poym.
Sci., 2007, 106, 3502

[262]

Vladimir I. Lozinsky, Irina V. Bakeeva, Elena P. Presnyak, Lilija

Damshkaln, Vitaly P. Zubov, J. Appl. Poym. Sci. 2007, 105, 2689.

[263]

Khairul Anuar Mat Amin, Khairiah Haji Badri, J. Appl. Poym. Sci., 2007, 105,
2488.

[264]

Mavani S. I., Mehta N. M., Parsania P. H, J. Appl. Poym. Sci., 2007, 106, 1228.

[265]

Jamal Mirbagheri, Mehdi Tajvidi, John C. Hermanson, Ismaeil Ghasemi, J.

Appl.Poym. Sci., 2007, 105, 3054.

[266]

Mohseni Garakani M., Arefazar A., Nazockdast N., J. Appl. Poym. Sci. 2007,
104, 2704.

[267]

Bandyopadhyay A., Sanker M., Bhowmick A.K., Rubber. Chem. Technol.,

2005, 78, 806.

[268]

Michael Alexandre, Philippe Dubois, Mater. Sci. Eng. 2000, 28,1

[269]

Komarneni S.J., J. Mater. Chem., 1992, 2, 1219.

[270]

Giannelis E.P., Adv. Mater., 1996, 8, 29.

[271]

Yariv S., Cross H., Eds., Organo-Clay Complexes and Interactions, Marcel
Dekker, New York, 2002.

[272]

Van Olphen, H., An introduction to Clay Colloid Chemistry, 2nd ed., Wiley,
New York, 1973.

G.

61

Chapter-1
[273]

Mark J.E., Polym. Eng. Sci. 1996, 36, 2905.

[274]

Wen J., Wilkes G.L. Chem. Mater. 1996, 8, 1667.

[275]

Von Werne T., Patten T.E., J. Am. Chem. Soc., 1999, 121, 7409.

[276]

Calvert P., Carbon Nanotubes, Editor, Ebbesen, T.W., CRC Press, Boca Raton,
1992.

[277]

Dresselhaus M.S., Dresselhaus Avouris P Carbon Nanotubes : Synthesis,

Structure, Properties and Applications, Topics of applied Physics, vol.80, Eds.,
Springer-Verlag, Heidelberg, 2001.

[278]

Favier V., Canova G.R., Shrivastava S.C., Cavaille J.Y., Polym. Eng. Sci.,
1997, 37, 1732.

[279]

Chazeau L., Canova G.R.,, Cavaille J.Y., Dendievel R., Boutherin B., J. Appl.
Poym. Sci., 1999, 71, 1797.

[280]

Nastase F., Ioan Stamatin, Claudia Nastase D. Mihaiescu D., Moldovan A.,
Prog. Solid State Chem., 2006, 34, 191.

[281]

Dong-ming Qi, Yong-zhong Bao, Zhi-xue Weng , Zhi-ming Huang., Polymer,

2006, 47, 4622.

[282]

Xiaoming Yang, Tingyang Dai, Yun Lu, Polymer, 2006, 47, 441.

[283]

Zhenyu Wang, Enhou Han , Wei Ke., Polym. Degrad. Stab. 2006, 91, 1937.

[284]

Patel S., Bandyopadhyay A., Vijayabaskar V., Anil K. Bhowmick, Polymer,

2005, 46, 8079.

[285]

Abhijit Bandyopadhyay, Mousumi De Sarkar, Anil K. Bhowmick, 2005, 95,

1418.

[286]

Wolff S, Goer U,. Wang M.J Eur. Rubber J., 1994, 16, 1619.

[287]

Medalia A.I, Kraus G in `Science and Technology of Rubber' Eds. J.E. Mark,
Erman, and R.F. Eirich, Academic Press, New York, 1994, Chapter 8, 387.

[288]

Wagner M.P., Rubber Chem. Technol., 1976, 49, 703

[289]

Wolff S., Wang M.J., Tan E.H., Kautsch. Gummi Kunstst., 1994, 47, 102.

[290]

Okel T.A., Patkar S.D., Bice J.A.E, Prog. Rubber Plast. Technol., 1999, 15, 1.

62

Introduction

[291]

Lee J.D., Concise inorganic chemistry, Fourth edn., Chapman and Hall ltd.
London, 1991, Chapter 13, 429.

[292]

Werner Hofman, In: Rubber Technology Handbook' -Ed. Anser Publishers,

Munich, 1989, Chapter 4, 284.

[293]

Blow C.M, "Rubber Technology and Manufacture" Ed. C.M. Blow, Published for
the Institution of Rubber industry- Butterworths, London, 1971, Chapter. 7, 227.

[294]

Krysztafkiewicz A., Chemia Stosowana, 1984, 28, 477.

[295]

Krysztafkiewicz A., Chemia Stosowana, 1987, 31, 127.

[296]

Marciniec B., Krysztafkiewicz A, Domka L., Colloid Polym. Sci., 1983,

261, 306.

[297]

Stober W., Fink A., Bohn E., J. Colloid Interface Sci., 1968, 26, 62.

[298]

Ulrich Schubert, Nichola Husing, Synthesis of Inorganic Materials, Wiley,

New York.

[299]

Kenneth J. Klabunde, Nanoscale Materials in Chemistry, Wiley

interscience.

[300] Tapasi Kotoky, Dolui S. K., J. Sol. Gel. Sci. Technol., 2004, 20, 107.

********YZ*******

63